Process for producing unitary graphene materials

ABSTRACT

A process for producing a unitary graphene material, comprising: (a) preparing a graphene oxide (GO) gel having GO molecules dissolved in a fluid medium wherein the GO molecules contain higher than 20% by weight of oxygen; (b) dispensing and depositing a layer of GO gel onto a surface of a substrate to form a layer of deposited GO gel thereon, wherein the dispensing and depositing procedure includes shear-induced thinning; (c) removing the fluid medium from the deposited GO gel to form a GO layer having an inter-plane spacing d 002  of 0.4 nm to 1.2 nm as determined by X-ray diffraction; and (d) heat treating the GO layer to form the unitary graphene material at a heat treatment temperature higher than 100° C. to an extent that d 002  is decreased to a value of 0.3354 nm to 0.4 nm and the oxygen content is decreased to less than 5% by weight.

The present invention claims the benefits of the following co-pending patent applications:

-   A. Zhamu, et al., “Graphene Oxide Gel Bonded Graphene Composite     Films and Processes for Producing Same,” U.S. patent application     Ser. No. 13/385,813 (Mar. 8, 2012). -   Aruna Zhamu, Mingchao Wang, Wei Xiong, and Bor Z. Jang, “Unitary     Graphene Layer or Graphene Single Crystal,” U.S. patent application     Ser. No. 13/694,356 (Nov. 26, 2012). -   Aruna Zhamu, Mingchao Wang, Wei Xiong, and Bor Z. Jang, “Unitary     Graphene Matrix Composites Containing Carbon or Graphite Fillers,”     U.S. patent application Ser. No. 13/694,468 (Dec. 5, 2012). -   Aruna Zhamu, Yi-jun Lin, Mingchao Wang, Wei Xiong, and Bor Z. Jang,     “Unitary Graphene Material-Based Integrated Finned Heat Sink,” U.S.     patent application Ser. No. 13/694,791 (Jan. 7, 2013).

FIELD OF THE INVENTION

The present invention relates generally to the field of graphitic materials for heat dissipation applications and, more particularly, to a process for producing a unitary graphene material. This unitary graphene material exhibits a combination of exceptionally high thermal conductivity, high electrical conductivity, high mechanical strength, good surface scratch resistance, and good hardness.

BACKGROUND OF THE INVENTION

Advanced thermal management materials are becoming critical for today's microelectronic, photonic, and photovoltaic systems. For instance, as new and more powerful chip designs and light-emitting diode (LED) systems are introduced, they consume more power and generate more heat. This has made thermal management a crucial issue in today's high performance systems. Systems ranging from active electronically scanned radar arrays, web servers, large battery packs for personal consumer electronics, wide-screen displays, and solid-state lighting devices all require high thermal conductivity materials that can dissipate heat more efficiently. On the other hand, the devices are designed and fabricated to become increasingly smaller, thinner, lighter, and tighter. This further increases the difficulty of thermal dissipation. Actually, thermal management challenges are now widely recognized as the key barriers to industry's ability to provide continued improvements in device and system performance.

One group of materials potentially suitable for heat dissipation applications is the graphitic carbon or graphite. Carbon is known to have five unique crystalline structures, including diamond, fullerene (0-D nano graphitic material), carbon nano-tube or carbon nano-fiber (1-D nano graphitic material), graphene (2-D nano graphitic material), and graphite (3-D graphitic material). The carbon nano-tube (CNT) refers to a tubular structure grown with a single wall or multi-wall. Carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs) have a diameter on the order of a few nanometers to a few hundred nanometers. Their longitudinal, hollow structures impart unique mechanical, electrical and chemical properties to the material. The CNT or CNF is a one-dimensional nano carbon or 1-D nano graphite material.

Bulk natural flake graphite is a 3-D graphitic material with each particle being composed of multiple grains (a grain being a graphite single crystal or crystallite) with grain boundaries (amorphous or defect zones) demarcating neighboring graphite single crystals. Each grain is composed of multiple graphene planes that are oriented parallel to one another. A graphene plane in a graphite crystallite is composed of carbon atoms occupying a two-dimensional, hexagonal lattice. In a given grain or single crystal, the graphene planes are stacked and bonded via van der Waal forces in the crystallographic c-direction (perpendicular to the graphene plane or basal plane). Although all the graphene planes in one grain are parallel to one another, typically the graphene planes in one grain and the graphene planes in an adjacent grain are different in orientation. In other words, the orientations of the various grains in a graphite particle typically differ from one grain to another.

A graphite single crystal (crystallite) per se is anisotropic with a property measured along a direction in the basal plane (crystallographic a- or b-axis direction) being dramatically different than if measured along the crystallographic c-axis direction (thickness direction). For instance, the thermal conductivity of a graphite single crystal can be up to approximately 1,920 W/mK (theoretical) or 1,800 W/mK (experimental) in the basal plane (crystallographic a- and b-axis directions), but that along the crystallographic c-axis direction is less than 10 W/mK (typically less than 5 W/mK). Further, the multiple grains or crystallites in a graphite particle are typically all oriented along different directions. Consequently, a natural graphite particle composed of multiple grains of different orientations exhibits an average property between these two extremes (i.e. between5 W/mK and 1,800 W/mK.

It would be highly desirable in many applications to produce a bulk graphite particle (containing single or multiple grains) having sufficiently large dimensions and having all graphene planes being essentially parallel to one another along one desired direction. For instance, it is highly desirable to have one large-size graphite entity (e.g. a fully integrated or unitary layer of multiple graphene planes) having the c-axis directions of all the graphene planes being substantially parallel to one another and having a sufficiently large length and/or width for a particular application (e.g. >5 cm² for use as a heat-spreading sheet on a CPU of a smart phone) and a sufficient thickness (e.g. >10 μm and more preferably >20 μm) to impart rigidity to a thin film for easy handling. It would be further desirable if such a “giant graphite particle” has only one grain or few grains (thus, no or little grain boundaries) and has few or no defects therein to impede the flow of electrons and phonons. Thus far, it has not been possible to produce this type of large-size unitary graphene entity from existing natural or synthetic graphite particles.

The constituent graphene planes of a graphite crystallite can be exfoliated and extracted or isolated from a graphite crystallite to obtain individual graphene sheets of carbon atoms provided the inter-planar van der Waals forces can be overcome. An isolated, individual graphene sheet of carbon atoms is commonly referred to as single-layer graphene. A stack of multiple graphene planes bonded through van der Waals forces in the thickness direction with an inter-graphene plane spacing of 0.3354 nm is commonly referred to as a multi-layer graphene. A multi-layer graphene platelet has up to 300 layers of graphene planes (<100 nm in thickness), but more typically up to 30 graphene planes (<10 nm in thickness), even more typically up to 20 graphene planes (<7 nm in thickness), and most typically up to 10 graphene planes (commonly referred to as few-layer graphene in scientific community). Single-layer graphene and multi-layer graphene sheets are collectively called “nano graphene platelets” (NGPs). Graphene sheets/platelets or NGPs are a new class of carbon nano material (a 2-D nano carbon) that is distinct from the 0-D fullerene, the 1-D CNT, and the 3-D graphite.

Our research group pioneered the development of graphene materials and related production processes as early as 2002: (1) B. Z. Jang and W. C. Huang, “Nano-scaled Graphene Plates,” U.S. Pat. No. 7,071,258 (Jul. 4, 2006), application submitted on Oct. 21, 2002; (2) B. Z. Jang, et al. “Process for Producing Nano-scaled Graphene Plates,” U.S. patent application Ser. No. 10/858,814 (Jun. 3, 2004); and (3) B. Z. Jang, A. Zhamu, and J. Guo, “Process for Producing Nano-scaled Platelets and Nanocomposites,” U.S. patent application Ser. No. 11/509,424 (Aug. 25, 2006).

NGPs are typically obtained by intercalating natural graphite particles with a strong acid and/or oxidizing agent to obtain a graphite intercalation compound (GIC) or graphite oxide (GO), as illustrated in FIG. 1( a) (process flow chart) and FIG. 1( b) (schematic drawing). The presence of chemical species or functional groups in the interstitial spaces between graphene planes serves to increase the inter-graphene spacing (d₀₀₂, as determined by X-ray diffraction), thereby significantly reducing the van der Waals forces that otherwise hold graphene planes together along the c-axis direction. The GIC or GO is most often produced by immersing natural graphite powder (20 in FIGS. 1( a) and 100 in FIG. 1( b)) in a mixture of sulfuric acid, nitric acid (an oxidizing agent), and another oxidizing agent (e.g. potassium permanganate or sodium perchlorate). The resulting GIC (22 or 102) is actually some type of graphite oxide (GO) particles. This GIC is then repeatedly washed and rinsed in water to remove excess acids, resulting in a graphite oxide suspension or dispersion, which contains discrete and visually discernible graphite oxide particles dispersed in water. There are two processing routes to follow after this rinsing step:

Route 1 involves removing water from the suspension to obtain “expandable graphite,” which is essentially a mass of dried GIC or dried graphite oxide particles. Upon exposure of expandable graphite to a temperature in the range of typically 800-1,050° C. for approximately 30 seconds to 2 minutes, the GIC undergoes a rapid expansion by a factor of 30-300 to form “graphite worms” (24 or 104), which are each a collection of exfoliated, but largely un-separated graphite flakes that remain interconnected. A SEM image of graphite worms is presented in FIG. 2( a).

In Route 1A, these graphite worms (exfoliated graphite or “networks of interconnected/non-separated graphite flakes”) can be re-compressed to obtain flexible graphite sheets or foils (26 or 106) that typically have a thickness in the range of 0.1 mm (100 μm)-0.5 mm (500 μm). Alternatively, one may choose to use a low-intensity air mill or shearing machine to simply break up the graphite worms for the purpose of producing the so-called “expanded graphite flakes” (108) which contain mostly graphite flakes or platelets thicker than 100 nm (hence, not a nano material by definition).

Exfoliated graphite worms, expanded graphite flakes, and the recompressed mass of graphite worms (commonly referred to as flexible graphite sheet or flexible graphite foil) are all 3-D graphitic materials that are fundamentally different and patently distinct from either the 1-D nano carbon material (CNT or CNF) or the 2-D nano carbon material (graphene sheets or platelets, NGPs). Flexible graphite (FG) foils can be used as a heat spreader material, but exhibiting a maximum in-plane thermal conductivity of typically less than 500 W/mK (more typically <300 W/mK) and in-plane electrical conductivity no greater than 1,500 S/cm. These low conductivity values are a direct result of the many defects, wrinkled or folded graphite flakes, interruptions or gaps between graphite flakes, and non-parallel flakes (e.g. SEM image in FIG. 2( b)). Many flakes are inclined with respect to one another at a very large angle (e.g. mis-orientation of 20-40 degrees).

In Route 1B, the exfoliated graphite is subjected to high-intensity mechanical shearing (e.g. using an ultrasonicator, high-shear mixer, high-intensity air jet mill, or high-energy ball mill) to form separated single-layer and multi-layer graphene sheets (collectively called NGPs, 33 or 112), as disclosed in our U.S. application Ser. No. 10/858,814. Single-layer graphene can be as thin as 0.34 nm, while multi-layer graphene can have a thickness up to 100 nm, but more typically less than 20 nm.

Route 2 entails ultrasonicating the graphite oxide suspension for the purpose of separating/isolating individual graphene oxide sheets from graphite oxide particles. This is based on the notion that the inter-graphene plane separation has been increased from 0.3354 nm in natural graphite to 0.6-1.1 nm in highly oxidized graphite oxide, significantly weakening the van der Waals forces that hold neighboring planes together. Ultrasonic power can be sufficient to further separate graphene plane sheets to form separated, isolated, or discrete graphene oxide (GO) sheets. These graphene oxide sheets can then be chemically or thermally reduced to obtain “reduced graphene oxides” (RGO) typically having an oxygen content of 0.001%-40% by weight, more typically 0.01%-5% by weight, most typically and highly desirably less than 2% by weight.

For the purpose of defining the claims of the instant application, NGPs include discrete sheets/platelets of single-layer and multi-layer graphene, graphene oxide, or reduced graphene oxide with an oxygen content of 0-10% by weight, more typically 0-5% by weight, and preferably 0-2% by weight. Pristine graphene has essentially 0% oxygen. Graphene oxide (including RGO) can have 0.001%-46% by weight of oxygen.

The GO molecules in graphene oxide gel, to be described in detail later, typically contains 20-50% by weight oxygen (more typically 30-47%) immediately after removal of the liquid from the GO gel, but prior to a subsequent heat treatment. The GO gel refers to a homogeneous solution of highly hydrophilic aromatic molecules (graphene oxide molecules bearing oxygen-containing groups, such as —OH, —COOH, and >O, on molecular planes or at the edges) that are dissolved (not just dispersed) in a liquid (e.g. acidic water). The GO gel per se does not contain visibly discernible or discrete graphene or GO particles in the form of solid sheets or platelets. These GO molecules and the dispersing liquid medium have comparable indices of refraction, making the resulting gel optically transparent or translucent (if the proportion of GO molecules are bot excessively high), or showing lightly brown color. In contrast, the simple mixture of original graphite particles or discrete NGP sheets/platelets with acids and/or water appears optically dark and totally opaque (even with only <0.1% solid particles suspended in the liquid medium). These particles or NGP platelets are simply dispersed (not dissolved) in the fluid medium.

These GO molecules in a GO gel are highly reactive and may be considered as “living giant molecules”. By contrast, the prior art solid sheets/platelets of graphene, GO, and RGO are essentially “dead” species. The GO gel can be formed into a shape with a proper shearing or compression stress (e.g. via casting or molding), dried (with liquid components partially or totally removed), and heat-treated under certain conditions to obtain a unitary graphene material, which is typically a single crystal, a poly-crystal with incomplete or poorly delineated grain boundaries, or a poly-crystal with very large grain sizes (very few grains). The heat treatment serves to chemically link these active or live GO molecules to form a 2-D or 3-D network of chemically bonded graphene molecules of essentially infinite molecular weights, and to drastically reduce the oxygen content of GO down to below 10% by weight, more typically <5%, further more typically <2%, and most typically <<1%. Only a trace amount of oxygen (practically 0%) can survive if the heat treatment temperature is sufficiently high and heat treatment time sufficiently long. This new and unique material called “unitary graphene material” will be further described in detail later.

Although the GO gel per se does not contain visibly discernible/discrete graphene sheets/platelets or NGPs (including “dead” GO sheets/platelets), one can intentionally add discrete graphene sheets/platelets, expanded graphite flakes, and other type of solid filler in the GO gel to form a mixture gel. This mixture gel may be dried and subjected to the same heat treatment to convert the live GO molecules into a unitary graphene material, also enabling these active molecules to chemically bond to the filler particles. This graphene oxide gel-derived graphene material, reinforced with a filler phase (e.g. discrete NGPs, CNTs and carbon fibers), constitutes the presently invented unitary graphene matrix composite as a readily mass-processible material.

It may be noted that flexible graphite foils (obtained by compressing or roll-pressing exfoliated graphite worms) for electronic device thermal management applications (e.g. as a heat sink material) have the following major deficiencies:

-   -   (1) As indicated earlier, flexible graphite (FG) foils exhibit a         relatively low thermal conductivity, typically <500 W/mK and         more typically <300 W/mK. By impregnating the exfoliated         graphite with a resin, the resulting composite exhibits an even         lower thermal conductivity (typically <<200 W/mK, more typically         <100 W/mK).     -   (2) Flexible graphite foils, without a resin impregnated therein         or coated thereon, are of low strength, low rigidity, and poor         structural integrity. The high tendency for flexible graphite         foils to get torn apart makes them difficult to handle in the         process of making a heat sink. As a matter of fact, the flexible         graphite sheets (typically 50-200 μm thick) are so “flexible”         that they are not sufficiently rigid to make a fin component         material for a finned heat sink.     -   (3) Another very subtle, largely ignored or overlooked, but         critically important feature of FG foils is their high tendency         to get flaky with graphite flakes easily coming off from FG         sheet surfaces and emitting out to other parts of a         microelectronic device. These highly electrically conducting         flakes (typically 1-200 μm in lateral dimensions and >100 nm in         thickness) can cause internal shorting and failure of electronic         devices.     -   (4) Both resin-free flexible graphite and resin-impregnated FG         (with resin impregnating step occurring before or after         roll-pressing) are not conducive to mass production of finned         heat sink structures. It is virtually impossible to use mass         production processes (such as extrusion, stamping, forging, and         die casting that are commonly used for making aluminum heat         sinks, or injection molding for making conductive         filler-reinforced plastic-based heat sinks) to make FG-based         heat sinks without some kind of subsequent bonding or assembling         operations. One has to manually attach individual fin members to         a core or base member. For instance, one may produce bonded fin         heat sink assemblies in which each fin in the assembly is         individually bonded into a heat sink base. A major shortcoming         of such heat sinks is their high cost. This cost is related         directly to the labor required to individually arrange each fin         on some sort of support or substrate (a base or core) and high         production cycle time. Further, bonding between a fin and a base         is not always reliable and the long-term reliability of flexible         graphite-based finned heat sinks is highly questionable.

Similarly, solid NGPs (including discrete sheets/platelets of pristine graphene, GO, and GRO), when packed into a film, membrane, or paper sheet (34 or 114) of non-woven aggregates, typically do not exhibit a high thermal conductivity unless these sheets/platelets are closely packed and the film/membrane/paper is ultra-thin (e.g. <1 μm, which is mechanically weak). This is reported in our earlier U.S. patent application Ser. No. 11/784,606 (Apr. 9, 2007). However, ultra-thin film or paper sheets (<10 μm) are difficult to produce in mass quantities, and difficult to handle when one tries to incorporate these thin films as a heat sink material. In general, a paper-like structure or mat made from platelets of graphene, GO, or RGO (e.g. those paper sheets prepared by vacuum-assisted filtration process) exhibit many defects, wrinkled or folded graphene sheets, interruptions or gaps between platelets, and non-parallel platelets (e.g. SEM image in FIG. 3( b)), leading to relatively poor thermal conductivity, low electric conductivity, and low structural strength. These papers or aggregates of discrete NGP, GO or RGO platelets alone (without a resin binder) also have a tendency to get flaky, emitting conductive particles into air.

Our earlier application (U.S. application Ser. No. 11/784,606) also disclosed a mat, film, or paper of NGPs infiltrated with a metal, glass, ceramic, resin, and CVD carbon matrix material (graphene sheets/platelets being the filler or reinforcement phase, not the matrix phase in this earlier application). Haddon, et al. (US Pub. No. 2010/0140792, Jun. 10, 2010) also reported NGP thin-film paper (aggregates of isolated platelets) and NGP-reinforced polymer matrix composites for thermal management applications. The processes used by Haddon et al to produce NGPs are identical to those disclosed much earlier by us (Jang, et al. U.S. patent application Ser. No. 10/858,814 (Jun. 3, 2004)). The NGP-reinforced polymer matrix composites, as an intended thermal interface material, have very low thermal conductivity, typically <<2 W/mK. The NGP films of Haddon, et al are essentially non-woven aggregates of discrete graphene platelets, identical to those of our earlier invention (U.S. application Ser. No. 11/784,606). Again, these aggregates have a great tendency to have graphite particles flaking and separated from the film surface, creating internal shorting problem for the electronic device containing these aggregates. They also exhibit low thermal conductivity unless made into thin films (10 nm-300 nm, as reported by Haddon, et al) which are very difficult to handle in a real device manufacturing environment. Balandin, et al (US Pub. No. 2010/0085713, Apr. 8, 2010) also disclosed a graphene layer produced by CVD deposition or diamond conversion for heat spreader application. More recently, Kim, et al (N. P. Kim and J. P. Huang, “Graphene Nanoplatelet Metal Matrix,” US Pub. No. 2011/0108978, May 10, 2011) reported metal matrix infiltrated NGPs. However, the metal matrix is too heavy and the resulting metal matrix composite does not exhibit a high thermal conductivity. More significantly, all these prior art materials and related processes are not amenable to mass production of heat-dissipation structures, such as finned heat sinks, cost-effectively. In fact, there has been no known report on using these materials for finned heat sink applications.

Another prior art material for thermal management applications is the pyrolitic graphite film. The lower portion of FIG. 1( a) illustrates a typical process for producing prior art pyrolitic graphitic films from a polymer. The process begins with carbonizing a polymer film 46 (e.g. polyimide) at a carbonization temperature of 400-1,000° C. under a typical pressure of 10-15 Kg/cm² for 2-10 hours to obtain a carbonized material 48, which is followed by a graphitization treatment at 2,500-3,200° C. under an ultrahigh pressure of 100-300 Kg/cm² for 1-24 hours to form a graphitic film 50. It is technically utmost challenging to maintain such an ultrahigh pressure at such an ultrahigh temperature. This is a difficult, slow, tedious, energy-intensive, and extremely expensive process. Furthermore, carbonization of certain polymers (e.g. polyacrylonitrile) involves the emission of toxic species.

A second type of pyrolytic graphite is produced by high temperature decomposition of hydrocarbon gases in vacuum followed by deposition of the carbon atoms to a substrate surface. This vapor phase condensation of cracked hydrocarbons is essentially a chemical vapor deposition (CVD) process. In particular, highly oriented pyrolitic graphite (HOPG) is the material produced by the application of uniaxial pressure on deposited pyrocarbon or pyrolytic graphite at very high temperatures (typically 3,000-3,300° C.). This entails a thermo-mechanical treatment of combined and concurrent mechanical compression and ultra-high temperature for an extended period of time in a protective atmosphere; a very expensive, energy-intensive, and technically challenging process. The process requires ultra-high temperature equipment (with high vacuum, high pressure, or high compression provision) that is not only very expensive to make but also very expensive and difficult to maintain. Even with such extreme processing conditions, the resulting PG (including HOPG) still possesses many defects, grain boundaries, and mis-orientations (neighboring graphene planes not parallel to each other), resulting in less-than-satisfactory in-plane properties. Typically, the best prepared HOPG sheet or block remains far from being a graphite single crystal; instead, it typically still contains many grains or crystals and a vast amount of grain boundaries and defects. All PG film production processes do not allow for impregnation of a resin matrix. PG or HOPG films, being weak, non-rigid, and not easily processable suffer from the same shortcomings as flexible graphite intended for use to construct finned heat sinks.

Similarly, the most recently reported graphene thin film (<2 nm) prepared by catalytic CVD of hydrocarbon gas (e.g. C₂H₄) on Ni or Cu surface is not a single-grain crystal, but a poly-crystalline structure with many grain boundaries and defects. With Ni or Cu being the catalyst, carbon atoms obtained via decomposition of hydrocarbon gas molecules at 800-1,000° C. are deposited onto Ni or Cu foil surface to form a sheet of single-layer or few-layer graphene that is poly-crystalline. The grains are typically much smaller than 100 μm in size and, more typically, smaller than 10 μm in size. These graphene thin films, being optically transparent and electrically conducting, are intended for applications such as the touch screen (to replace indium-tin oxide or ITO glass) or semiconductor (to replace silicon, Si). However, these ultra-thin polycrystalline graphene films are not sufficiently thermally conducting (too many grains or too much grain boundaries, and all grains being oriented in different directions) and not sufficiently thick for use as a heat sink or heat spreader material. Furthermore, the Ni- or Cu-catalyzed CVD process does not lend itself to the deposition of more than 5-10 graphene planes (typically <2-4 nm) beyond which the underlying Ni or Cu catalyst can no longer provide any catalytic effect. There has been no experimental evidence to indicate that CVD graphene layer thicker than 5 or 10 nm is possible. Further, CVD is not conducive to the fabrication of a heat sink that is typically complex in shape.

Thus, it is an object of the present invention to provide a process for producing graphene oxide (GO) gel-derived unitary graphene material (monolithic graphene entity) or its composite version (containing, for instance, a carbon/graphite filler phase dispersed in or bonded by a unitary graphene matrix material derived from a GO gel), which exhibits a thermal conductivity comparable to or greater than the thermal conductivities of the PG (including HOPG), CVD graphene film, and/or flexible graphite (including resin-impregnated FG).

This thermally and electrically conductive graphene monolith or graphene matrix composite can be used to produce finned heat sinks cost effectively in large quantities, using commonly used, less complex, and easier-to-control processes with readily available, inexpensive equipment.

It is another object of the present invention to provide a process for producing GO-derived unitary graphene entity and graphene matrix composite that exhibit a combination of exceptional thermal conductivity, electrical conductivity, mechanical strength, surface hardness, and scratch resistance unmatched by any material of comparable thickness range.

It is a specific object of the present invention to provide a highly conductive unitary graphene material or graphene matrix composite that meets the following technical requirements (a) a thermal conductivity greater than 600 W/mK (preferably greater than 1,000 W/mK, and further preferably greater than 1,700 W/mK); (b) an electrical conductivity greater than 2,000 S/cm (preferably >3,000 S/cm, more preferably >5,000 S/cm, even more desirably >10,000 S/cm, and most preferably >15,000 S/cm); (c) Rockwell surface hardness value >60 (preferably >80); and/or (d) a tensile or flexural strength greater than 80 MPa (preferably >100 MPa, more preferably >150 MPa, and most preferably >200 MPa). No prior art material meets this set of technical requirements.

This new class of materials (i.e., a GO gel-derived unitary graphene monolithic and the unitary graphene matrix composite) has the following characteristics (separately or in combination) that distinguish themselves from PG, HOPG, CVD graphene film, flexible graphite sheets, flexible graphite composite, paper/film/membrane of discrete graphene/GO/RGO sheets/platelets, and conventional graphene/GO/RGO platelet-reinforced resin matrix composite, metal matrix composite, and carbon matrix composites:

(1) This unitary graphene material is an integrated graphene entity that is either a graphene single crystal (single grain only) or a poly-crystal (multiple grains but typically having incomplete grain boundaries or having exceptionally large grains). Typically and preferably, with some compression or shearing stresses exerted on the GO during shaping and subsequent heat treating, the unitary graphene material has all the graphene planes in all the grains being essentially oriented parallel to one another (i.e., the crystallographic c-axis of all grains pointing in an identical direction).

(2) The unitary graphene matrix is an integrated graphene entity that is not an aggregate or stack of multiple discrete graphite flakes or discrete platelets of graphene/GO/RGO, and does not contain any discernible or discrete flake/platelet derived from the original GO gel.

(3) This integrated graphene matrix is not made by bonding discrete flakes/platelets together with a binder or adhesive. Instead, GO molecules in the GO gel are chemically active and live species capable of chemically merging with one another mainly in an edge-to-edge manner (forming 2-D giant graphene molecules), but possibly also with adjacent GO molecules below or above (forming 3-D network of graphene chains). Through joining or forming of covalent bonds with one another, the GO molecules are adhered into an integrated graphene entity (the unitary graphene material), without using any externally added linker or binder molecules or polymers. In the presence of discrete carbon/graphite/graphene filler particles (e.g. carbon black particles, CNTs, and NGPs), the GO molecules are also capable of acting as a binder or adhesive that chemically bonds these carbon/graphite filler particles together to form a strong composite.

(4) This unitary or monolithic graphene matrix (a single crystal or poly-crystal with essentially all graphene planes having an identical crystallographic c-axis) is derived from a GO gel, which is in turn obtained from heavy oxidation of natural graphite or artificial graphite particles originally having multiple graphite crystallites. Prior to being chemically oxidized to become GO gel, these starting or original graphite crystallites have an initial length (L_(a) in the crystallographic a-axis direction), initial width (L_(b) in the b-axis direction), and thickness (L_(c) in the c-axis direction). The resulting unitary graphene entity typically has a length or width significantly greater than the L_(a) and L_(b) of the original graphite crystallites.

(5) It may be noted that there has been numerous reports on “graphene composites.” However, these “graphene composites” make use of discrete pristine graphene sheets, graphene oxide platelets, or reduced graphene oxide platelets as the reinforcement phase, which is dispersed in a matrix material selected from a resin (to form a resin matrix composite), a metal (metal matrix composite), a carbon (carbon matrix composite), a glass (glass matrix composite), or a ceramic (ceramic matrix composite). In these prior art “graphene composites,” graphene sheets/platelets are the discrete and dispersed phase, not the matrix phase (i.e., not the continuous phase that bonds and protects the dispersed phase). These discrete graphene sheets/platelets are the dispersed phase bonded and protected by a matrix material, such as a resin, metal, carbon (CVD carbon, amorphous carbon, or polymeric carbon), glass, or ceramic. In stark contrast or completely oppositely, in the presently invented unitary graphene matrix composite, graphene is the matrix material that serves to bond, adhere, and protect the dispersed filler phase, such as CNT and carbon black (CB) particles. CNT or CB particles are dispersed in and protected by the unitary graphene matrix. The graphene matrix is a continuous, unified, or integrated material phase.

The present invention also provides a cost-effective method or process for producing a GO gel-derived unitary graphene entity and the graphene matrix composite on a continuous or roll-to-roll basis.

Another object of the present invention is to provide a cost-effective process for producing a GO-derived graphene monolith or a graphene matrix composite that exhibits a combination of exceptional thermal conductivity, electrical conductivity, mechanical strength, surface hardness, and scratch resistance.

In particular, the present invention provides a fast, scalable process capable of mass-producing unitary or monolithic graphene or graphene matrix composites from a GO gel. Advantageously and surprisingly, conventional mass production techniques, such as die casting, injection molding, compression molding, resin-transfer molding, and extrusion, can be adapted for cost-effectively producing these materials.

This process involves significantly lower heat treatment temperatures as compared with the processes for producing pyrolytic graphite (including HOPG) from either carbonized polymers (e.g. polyimide) or the CVD graphite. The presently invented process is simpler (hence, more reliable), less energy-intensive, and highly scalable.

SUMMARY OF THE INVENTION

The present invention provides a process for producing a unitary graphene material, the process comprising: (a) preparing a graphene oxide gel having graphene oxide molecules dispersed in a fluid medium wherein the graphene oxide molecules contain an oxygen content higher than 20% by weight; (b) dispensing and depositing a layer of graphene oxide gel onto a surface of a supporting substrate to form a deposited graphene oxide gel thereon, wherein the dispensing and depositing procedure includes shear-induced thinning of the graphene oxide gel; (c) partially or completely removing the fluid medium from the deposited graphene oxide gel layer to form a graphene oxide layer having an inter-plane spacing d₀₀₂ of 0.4 nm to 1.2 nm as determined by X-ray diffraction and an oxygen content no less than 20% by weight; and (d) heat treating the graphene oxide layer to form said unitary graphene material at a heat treatment temperature higher than 100° C. to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.4 nm and the oxygen content is decreased to less than 5% by weight.

Shear-induced thinning in step (b) means the GO gel is subjected to a shear stress during processing and a viscosity of the GO gel is reduced during and/or after the application of such a shear stress. As an example, the shear stress can be encountered in a situation as simple as a “doctor's blade” that guides the spreading of GO gel over a glass surface during a manual casting process. As another example, an effective shear stress is created in an automated roll-to-roll coating process in which a “knife-on-roll” configuration dispenses GO over a moving solid substrate, such as a plastic film. The relative motion between this moving film and the coating knife creates such a shear stress.

This shear-induced thinning is a critically important step in the production of the presently invented unitary graphene material due to the surprising observation that shear-induced thinning enables the GO molecules to align themselves along a particular direction (e.g. X-direction) or two particular directions (e.g. X- and Y-directions) to produce preferred orientations. Further surprisingly, these preferred orientations are preserved and often further enhanced during the subsequent heat treatment to produce the unitary graphene material. Most surprisingly, such preferred orientations are essential to the eventual attainment of exceptionally high thermal conductivity, electrical conductivity, and mechanical strength of the resulting unitary graphene material along a desired direction. These great properties in this desired direction could not be obtained without such a shear stress-induced orientation control.

In one embodiment, the graphene oxide gel is obtained by immersing powders or filaments of a graphitic material in an oxidizing liquid medium (e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel. The graphitic material may be selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof. When the graphite powders or filaments are mixed in the oxidizing liquid medium, the resulting slurry initially appears completely dark and opaque. The resulting mass is simply a heterogeneous suspension of solid particles dispersed (not dissolved) in a liquid medium. When the oxidation of graphite proceeds at a reaction temperature for a sufficient length of time under a controlled pH condition, the reacting mass can eventually turn optically translucent, transparent (if sufficiently dilute), or uniform brown color which also looks and behaves like a gel. This heavy oxidation-induced graphene oxide gel is composed of graphene oxide molecules uniformly dissolved in the liquid medium. We observe that even if the initial solid graphite powder particles dispersed in water occupy a proportion as low as 0.1% by weight or lower, the suspension is heterogeneous and looks completely dark and opaque. In contrast, the GO gel is a homogeneous solution. Even when the GO molecule content exceeds 1% by weight, the GO gel can appear translucent or transparent.

The graphene oxide molecules in the GO gel, prior to any subsequent heat treatment, have an oxygen content no less than 20% by weight (more typically greater than 30% by weight, and most typically from 40-50% by weight) and their molecular weights are typically less than 43,000 g/mole (often less than 4,000 g/mole, but typically greater than 200 g/mole) while in a gel state. The graphene oxide gel is composed of graphene oxide molecules dissolved (not just dispersed) in an acidic medium having a pH value of typically no higher than 5.

Subsequently, the GO gel is formed into a shape (e.g. cast film on a solid substrate or sheared mass in a mold cavity) with the liquid component in the GO gel being partially or completely removed to obtain at least partially dried GO mass containing well-packed and well-aligned live GO molecules.

In one embodiment, the graphene oxide molecules in step (a) contain an oxygen content higher than 30% by weight.

In another embodiment, step (c) includes forming a graphene oxide layer having an inter-plane spacing d₀₀₂ of 0.4 nm to 0.7 nm and an oxygen content no less than 20% by weight; and step (d) includes heat-treating the graphene oxide layer to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.36 nm and the oxygen content is decreased to less than 2% by weight.

In still another embodiment, the graphene oxide gel has a viscosity greater than 2,000 cP (centipoise) when measured at 20° C. prior to the shear-induced thinning procedure, but the viscosity is reduced to below 2,000 cP (or even below 1,000 cP) during or after shear-induced thinning. In still another embodiment, the graphene oxide gel has a viscosity greater than 5,000 cP when measured at 20° C. prior to shear-induced thinning, but is reduced to below 5,000 cps (preferably and typically below 2,000 cP or even below 1,000 cP) during or after shear-induced thinning. Preferably, the graphene oxide gel has a viscosity from 500 cP to 500,000 cP when measured at 20° C. prior to shear-induced thinning.

Preferably, the graphene oxide gel has a viscosity less than 5,000 cP (preferably less than 2,000 cP and further preferably less than 1,000 cP) when measured at 20° C. after shear-induced thinning. In general, the graphene oxide gel has a viscosity that decreases by at least 10 times when a shear rate is increased to a finite extent at 20° C. The shear-induced thinning may be conducted via any of a wide variety of procedures, including coating, casting, injection molding, compression molding, resin-transfer molding, extrusion, pultrusin, or filament-winding.

The dried GO mass after deposition or molding is then subjected to a properly programmed heat treatment that can be divided into four distinct temperature regimes. The presently invented unitary graphene material can be obtained by heat-treating the dried GO mass with a temperature program that covers at least the first regime, more commonly covers the first two regimes, still more commonly the first three regimes, and most commonly all the 4 regimes (the latter being implemented to achieve the highest conductivity):

-   Regime 1: 100° C.-500° C. (the thermal reduction regime); Oxygen     content reduced from typically 30-50% to 5-6%, resulting in a     reduction of inter-graphene spacing from approximately 0.6-1.0 nm to     approximately 0.4 nm and an increase in in-plane thermal     conductivity of a consolidated thin film from approximately 100 to     450 W/mK. -   Regime 2: 500° C.-1,250° C. (the chemical linking regime); Oxygen     content reduced to typically 0.7% (<<1%), resulting in a reduction     of inter-graphene spacing to approximately 0.345 nm, an increase in     in-plane thermal conductivity of a unitary graphene thin film to     1,400-1,500 W/mK, and/or in-plane electrical conductivity to     3,000-4,000 S/cm. -   Regime 3: 1,250° C.-2,000° C. (the ordering and re-graphitization     regime); Oxygen content reduced to typically 0.01%, resulting in a     reduction of inter-graphene spacing to approximately 0.337 nm     (degree of graphitization from 1% to approximately 80%) and improved     degree of ordering, an increase in in-plane thermal conductivity of     a unitary graphene thin film to >1,680 W/mK, and/or in-plane     electrical conductivity to 5,000-7,000 S/cm. -   Regime 4: 2,000° C.-3,000° C. (the re-crystallization and perfection     regime); Oxygen content reduced to typically from near 0%-0.001%,     resulting in a reduction of inter-graphene spacing to approximately     0.3354 nm (degree of graphitization from 80% to nearly 100%) and     perfection of crystal structure and orientation, an increase in     in-plane thermal conductivity of a unitary graphene thin film     to >1,800 W/mK, and in-plane electrical conductivity to     15,000-25,000 S/cm.

The degree of graphitization, g, was calculated from the X-ray diffraction pattern using Mering's Eq, d₀₀₂=0.3354 g+0.344 (1−g), where d₀₀₂ is the interlayer spacing of graphite or graphene crystal in nm. This equation is valid only when d₀₀₂ is no greater than 0.3440 nm. The unitary graphene material having a d₀₀₂ higher than 0.3440 nm reflects the presence of oxygen-containing functional groups (such as —OH, >O, and —COOH on graphene molecular plane surfaces) that act as a spacer to increase the inter-graphene spacing.

Another structural index that can be used to characterize the degree of ordering of the presently invented unitary graphene material or related graphite crystals is the “mosaic spread” value, which is expressed by the full width at half maximum of the (002) or (004) reflection in a X-ray diffraction intensity curve. This degree of ordering characterizes the graphite or graphene crystal size (or grain size), amounts of grain boundaries and other defects, and the degree of preferred grain orientation. A nearly perfect single crystal of graphite is characterized by having a mosaic spread value of 0.2-0.4. Most of our unitary graphene materials have a mosaic spread value in this range of 0.2-0.4 (with a heat treatment temperature no less than 2,000° C.). However, some values are in the range of 0.4-0.7 if the highest heat treatment temperature (TTT) is between 1,250 and 2,000° C., and in the range of 0.7-1.0 if the TTT is between 500 and 1,250° C.

It is very important to state that the presently invented process allows us to prepare unitary graphene materials from an ultra-thin thickness (e.g. 10 nm to 100 nm, and up to 1 μm thin films), through intermediate thickness (1 μm-500 μm thick films), and high thickness (>0.5 mm for a bulk material). This is a significant advantage that no other graphitic or graphene material processes could provide. For instance, flexible graphite sheets produced from exfoliated worms could not be thicker than 50 μm (mostly >100 μm). Polyimide-derived pyrolytic graphite film is typically limited to 20 μm-50 μm due to the nature of available precursor polymer dimensions and carbonization conditions. Catalytic CVD graphene cannot go over 5-10 nm in thickness. Non-catalytic CVD can be thicker, but the graphene sheets tend to be randomly oriented.

Thus, one embodiment of the invention is a process that can produce unitary graphene material layer having a thickness greater than 100 nm. Another embodiment is a process for producing a unitary graphene material having a thickness greater than 100 nm but less than 10 μm. Another embodiment is a process for producing a unitary graphene material thicker than 10 μm. Still another embodiment is a process for producing a unitary graphene material having a thickness greater than 100 μm, further preferably >500 μm. However, with a thickness greater than 500 μm or 0.5 mm, the degree of graphene plane orientation is not nearly as high as in a unitary graphene layer thinner than 0.5 mm.

A preferred embodiment of the present invention is a unitary graphene material or a unitary graphene material being reinforced with a filler or reinforcement phase, wherein the unitary graphene material exhibits a mosaic spread value less than 1.0. Preferably, the unitary graphene material exhibits a degree of graphitization no less than 40% and/or a mosaic spread value less than 0.7. Further preferably, the unitary graphene material exhibits a degree of graphitization no less than 80% and/or a mosaic spread value no greater than 0.4. Most preferably, the degree of graphitization is at least 99% and/or the mosaic spread value is from 0.2 to 0.4, representing a near perfect graphene single crystal having all graphene planes essentially perfectly parallel to one another.

The presently invented unitary graphene material can further contain a discrete filler or reinforcement phase dispersed in the unitary graphene material to form a unitary graphene matrix composite structure. The filler or reinforcement phase may contain a particle, filament, nano-tube, nano-wire, or nano-rod of a metal, ceramic, glass, polymer, carbon, graphite, or a combination thereof. Particularly desired filler or reinforcement phase is selected from a carbon or graphite fiber, carbon or graphite nano-fiber, carbon nano-tube, carbon nano-rod, meso-phase carbon particle, meso-carbon micro-bead, expanded graphite flake with a thickness greater than 100 nm, single-layer graphene sheet, multi-layer graphene platelet with a thickness less than 100 nm, exfoliated graphite or graphite worm, coke particle, needle coke, carbon black or acetylene black particle, activated carbon particle, or a combination thereof. The carbon, graphite, or graphene filler phase occupies a weight fraction of 0.01% to 99% (preferably from 10% to 70%) based on the total composite structure weight.

Preferably and typically, the carbon or graphite filler is chemically bonded by the unitary graphene matrix. It is most surprising that this unitary graphene matrix, prepared through the route of a GO gel, is capable of chemically bonding to a filler phase and that the constituent GO molecules in a GO gel mass are capable of chemically bonding and merging with one another to form an integrated 2-D or 3-D network of aromatic chains or giant graphene molecules of essentially infinite molecular weight, much like a 3-D network of cross-linked polymer chains. Chemical analyses, including various spectroscopy studies, have demonstrated that these chemically bonded graphene molecules contain a combination of sp² and sp³ electronic configurations.

It may be noted that the unitary graphene matrix material, when prepared alone without the presence of the carbon or graphite filler phase, can be made into a unitary graphene layer or graphene single crystal. This unitary graphene layer or graphene single crystal would contain closely packed and bonded parallel graphene planes having an inter-graphene plane spacing of 0.3354 to 0.40 nm (mostly between 0.3354 and 0.337 nm) and an oxygen content up to 10% by weight (mostly <<1%). This unitary graphene layer or graphene single crystal can be obtained from heat-treating a graphene oxide gel at a temperature higher than 100° C. (up to 500, 1,250, 2,000, or 3,000° C., depending upon the desired properties), wherein an average mis-orientation angle between two graphene planes is less than 10 degrees, preferably and typically less than 5 degrees. The graphene single crystal, prepared alone without the presence of a filler, refers to the single-grain or single-domain graphene or poly-crystalline structure (but having incomplete grain boundaries) in which most of the graphene planes in all grain(s) are essentially parallel to one another. This unitary graphene or graphene monolith contains therein no discrete graphite flake or graphene platelet derived from the graphene oxide gel. All graphene oxide molecules have been chemically merged, linked, and integrated into one single integral unit, hence the name “unitary graphene” entity.

The unitary graphene matrix or the graphene matrix composite typically and preferably has a physical density of at least 1.7 g/cm³ or a porosity level lower than 10%, and more typically and preferably has a physical density of at least 1.8 g/cm³ or a porosity level lower than 5%. The process enables us to produce unitary graphene material, without a filler, to reach a physical density most typically in the range of 2.0-2.25 g/cm³, approaching the theoretical density of a perfect graphite single crystal. Yet, no conventional graphite single crystal can be readily produced to have a dimension larger than a few microns (μm). We can produce this giant graphene particle wider or longer than tens of centimeters that are practically a single crystal. This is most astonishing.

In an embodiment, the graphene oxide gel is obtained from a graphitic material having a maximum original graphite grain size and the unitary graphene material is a single crystal or a poly-crystal graphene structure having a grain size larger than even the maximum original grain size. This maximum original grain size is the length or width of a graphene plane or a graphite crystallite in a graphite particle prior to being oxidized. The heat treatment involves extensive merging and linking of highly reactive GO molecules to form huge graphene planes and huge graphene domains (or grains) that are typically orders of magnitude greater than the original grain sizes.

In the unitary graphene matrix composite prepared in the presence of a filler phase, the chemically bonded graphene planes also can be parallel to one another (e.g. along a fiber axis direction). In the unitary graphene matrix composite, the unitary graphene matrix typically contains no complete grain boundary therein and contains no discrete or discernible graphene platelet derived from the original graphene oxide gel. Preferably and typically, the carbon or graphite filler is chemically bonded by the unitary matrix material in the composite (e.g. via covalent bonds).

The production of the graphene matrix composite typically begins with preparation of a mass of GO gel, which is then mixed with particles of the carbon/graphite filler phase to form a slurry mass. The slurry is formed into a desired shape (a finned heat sink or a component) supported by a die casting tool or mold cavity, preferably with a shear stress to facilitate orientation or alignment of aromatic GO molecules. Alternatively, the carbon/graphite filler phase is first formed into a porous preform (e.g. mat, paper, or fabric) of a desired heat sink shape, which is then impregnated with the GO gel. In either route, the liquid component of this GO gel is then partially or totally removed and, concurrently or sequentially, this GO material is subjected to a heat treatment. This heat treatment, also herein referred to as a chemical linking and re-graphitization treatment, thermally converts the GO molecules to an integrated graphene entity by chemically merging individual graphene oxide molecules primarily sideway in an edge-to-edge manner to form significantly larger graphene planes, but sometimes also chemically linking with the GO molecules below or above this graphene plane to form a 3-D molecular network. This 3-D molecular network can be broken and re-organized if the final heat treatment occurs at a sufficiently high temperature for an extended length of time.

Further alternatively, the carbon or graphite filler may be made into a form of fiber yarns or fiber bundles impregnated with the graphene oxide gel with shear-induced thinning, and the composite is made by forming the fiber yarns or bundles into a desired shape prior to heat treating. The desired shape can mean part of or an entire heat sink structure. It is highly surprising for us to observe that graphene oxide gel has an outstanding adhesive power that can bond the filler phase (e.g. carbon fibers or nano-tubes) together to form a composite of exceptional structural integrity.

The graphene oxide gel-derived unitary or monolithic graphene entity or the corresponding graphene matrix composite has a unique combination of outstanding thermal conductivity, electrical conductivity, mechanical strength, scratch resistance, and elimination of the possibility of having surface graphite flakes or particles to “flake off” (actually, there is no discrete flake/platelet to be peeled therefrom).

Further, the graphene oxide (GO) gel-derived unitary graphene matrix material or graphene matrix composite has the following novel, unique, and unprecedented characteristics (separately or in combination):

-   -   (1) The unitary graphene matrix material itself is an integrated         graphene object that is either a graphene single crystal or a         poly-crystal having multiple grains (but with incomplete or         poorly delineated grain boundaries, or huge grain sizes, having         negligible amount of grain boundaries that would otherwise         impede flow of electrons and phonons). When made into a         thin-film form (e.g. <200 μM thick) or formed under the         influence of a shear stress (to induce viscosity thinning), the         unitary graphene matrix is composed of multiple graphene planes         most of which are essentially oriented parallel to one another.     -   (2) In contrast to the paper-like sheets of expanded graphite         flakes or graphene platelets (e.g. those prepared by a         paper-making process), this integrated graphene entity (the         unitary graphene material) is not an aggregate or stack of         multiple discrete graphite flakes or discrete platelets of         graphene, GO, or RGO. This is a single graphene entity or         monolith, not a simple aggregate of multiple graphite flakes         (such as in FG foil) or graphene sheets/platelets (such as prior         art graphene paper/membrane/film). This unitary graphene entity         does not contain discrete graphite flakes or discrete graphene         platelets dispersed therein that are derived from the GO gel.         The GO molecules do not revert back to individual or discrete         graphene platelets or graphite flakes. Through chemical         inter-linking of GO molecules, re-graphitization, and         re-crystallization, the GO molecules and the original graphene         planes of hexagonal carbon atoms (constituting original graphite         particles) have completely lost their original individual         identity and have been united into one single entity (unitary         body or monolith).     -   (3) The integrated graphene entity is not made by gluing or         bonding discrete flakes/platelets together with a binder,         linker, or adhesive. Instead, GO molecules in the GO gel are         merged, mainly edge-to-edge through joining or forming of         covalent bonds with one another, into an integrated graphene         entity, without using any externally added linker or binder         molecules or polymers.     -   (4) This unitary or monolithic graphene entity is derived from a         GO gel, which is in turn obtained from natural graphite or         artificial graphite particles originally having multiple         graphite crystallites. Prior to being chemically oxidized, these         starting graphite crystallites have an initial length (L_(a) in         the crystallographic a-axis direction), initial width (L_(b) in         the b-axis direction), and thickness (L_(c) in the c-axis         direction). The resulting unitary graphene entity typically has         a length or width significantly greater than the L_(a) and L_(b)         of the original crystallites. Even the individual grains in a         poly-crystalline unitary graphene entity have a length or width         significantly greater than the L_(a) and L_(b) of the original         crystallites. They can be as large as the length or width of the         unitary graphene entity itself, not just 2 or 3 times higher         than the initial L_(a) and L_(b) of the original crystallites.         The unitary graphene layer or graphene single crystal typically         has a length or width no less than 10 μm, more typically no less         than 100 μm, and even more typically no less than 1 cm. They         often are extended to cover the entire width of the original GO         gel layer deposited on a substrate surface, which can be >100 cm         as desired.

The unitary graphene matrix material can have a thickness as low as 10 nm and can be as low as 2 nm, but the ultra-thin film thinner than 2 nm has the tendency to get fragmented when heated to a high temperature. The unitary graphene material preferably has a thickness >100 nm, more preferably >1 μm, even more preferably >10 μm. The unitary graphene matrix material alone or graphene matrix composite preferably has a thickness less than 200 μm for a heat spreader application, but it can be much thicker. The thickness range of 20-100 μm is particularly useful for mobile device thermal management applications.

A specific embodiment of the present invention is a process for producing a unitary graphene matrix composite, comprising: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium to form a homogeneous solution; (b) mixing a carbon or graphite filler phase in the graphene oxide gel to form a slurry; (c) dispensing the slurry into a cavity of a molding tool or forming the slurry into a desired shape under the influence of a shear stress to create shear-induced thinning and molecular orientation; (d) partially or completely removing the fluid medium from the slurry to form a composite precursor; and (e) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. (can be higher than 500° C., 1,250° C., 2000° C., or even 3,000° C. if so desired).

Another specific embodiment is a process for producing a unitary graphene matrix composite, comprising: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium to form a homogeneous solution; (b) combining a carbon or graphite filler phase with the graphene oxide gel to form an impregnated filler shape under the influence of a shear stress that induces viscosity thinning; (c) partially or completely removing the fluid medium from the impregnated filler shape to form a composite precursor; and (d) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. (can be higher than 500° C., 1,250° C., 2000° C., or even 3,000° C. if so desired).

The unitary graphene matrix composite shows a surprisingly high Rockwell hardness value, typically greater than 80 and often greater than 100. This is unprecedented since prior art flexible graphite foil, pyrolytic graphite, or bulk graphite does not show such a high hardness.

The unitary graphene matrix composite of the present invention can exhibit an electrical conductivity greater than 1,500 S/cm, a thermal conductivity greater than 600 W/mK, a physical density greater than 1.8 g/cm3, and/or a tensile strength greater than 80 MPa. With a higher re-graphitization temperature, the graphene monolithic can have an electrical conductivity greater than 3,000 S/cm, a thermal conductivity greater than 1,000 W/mK, a physical density greater than 1.9 g/cm3, and/or a tensile strength greater than 100 MPa. It can even exhibit an electrical conductivity greater than 5,000 S/cm, a thermal conductivity greater than 1,500 W/mK, a physical density greater than 2.0 g/cm³, and/or a tensile strength greater than 150 MPa.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 (a) A flow chart illustrating various prior art processes of producing exfoliated graphite products (flexible graphite foils and flexible graphite composites) and pyrolytic graphite (bottom portion), along with a process for producing graphene oxide gel 21, oriented GO layer 35, and unitary graphene material 37; (b) Schematic drawing illustrating the processes for conventional producing paper, mat, film, and membrane of simply aggregated graphite or NGP flakes/platelets. All processes begin with intercalation and/or oxidation treatment of graphitic materials (e.g. natural graphite particles).

FIG. 2 (a) A SEM image of a graphite worm sample after thermal exfoliation of graphite intercalation compounds (GICs) or graphite oxide powders; (b) An SEM image of a cross-section of a flexible graphite foil, showing many graphite flakes with orientations not parallel to the flexible graphite foil surface and also showing many defects, kinked or folded flakes.

FIG. 3 (a) A SEM image of a GO-derived graphene monolithic wherein multiple graphene planes (having a length/width of 30 nm-2 μm) in graphite particles, have been oxidized, exfoliated, re-oriented, and seamlessly merged into continuous-length graphene sheets or layers that can run for hundreds of centimeters wide or long (only a 120 μm or 0.12 mm width of a 25-cm wide unitary graphene material being shown in this SEM image); (b) A SEM image of a cross-section of a conventional graphene paper/film prepared from discrete graphene sheets/platelets using a paper-making process (e.g. vacuum-assisted filtration). The image shows many discrete graphene sheets being folded or interrupted (not integrated), with orientations not parallel to the film/paper surface and having many defects or imperfections; (c) Schematic drawing and an attendant SEM image to illustrate the formation process of a unitary graphene entity or graphene single crystal that is composed of multiple graphene planes that are parallel to one another and are chemically bonded in the thickness-direction or crystallographic c-axis direction; (d) Schematic of the prior art graphene poly-crystal obtained by CVD of hydrocarbon on a catalytic surface (e.g. Cu or Ni); (e) Schematic of a graphene single crystal of the present invention; (f) Schematic of another graphene single crystal of the present invention (a “poly-crystal” with incomplete grain boundaries); (g) One plausible chemical linking mechanism (only 2 GO molecules are shown as an example; a large number of GO molecules can be chemically linked together to form a unitary graphene layer).

FIG. 4 (a) Thermal conductivity values of the GO gel-derived single unitary graphene layer (▴), GO platelet paper (▪), and FG foil (♦) plotted as a function of the final heat treatment temperature for graphitization or re-graphitization; (b) Thermal conductivity values of the GO gel-derived unitary graphene layer (▪) and the polyimide-derived pyrolytic graphite (PG) heat-treated for one hour (x) and for 3 hours (▴), all plotted as a function of the final graphitization or re-graphitization temperature; (c) Electric conductivity values of the GO gel-derived unitary graphene layer (♦), GO platelet paper (▪), and FG foil (x) plotted as a function of the final graphitization or re-graphitization temperature; and (d) thermal conductivity values of unitary graphene layer only, unitary graphene matrix/CNT composite, GO paper (prepared from GO platelets not reaching a GO gel state), and GO/CNT paper or membrane. Note: symbol designations varied from (a) to (d).

FIG. 5 X-ray diffraction curves of (a) a GO film (dried GO gel), (b) GO film thermally reduced at 150° C. (partially re-duced), (c) highly reduced and re-graphitized GO film (a unitary graphene layer), (d) highly re-graphitized and re-crystallized GO single crystal (a more advanced unitary graphene material) showing a high-intensity (004) peak, and (e) a polyimide-derived HOPG with a HTT as high as 3,000° C.

FIG. 6 (a) Inter-graphene plane spacing measured by X-ray diffraction; (b) the oxygen content in the GO gel-derived unitary graphene layer; (c) correlation between inter-graphene spacing and the oxygen content; and (d) thermal conductivity of GO gel-derived unitary graphene layer and flexible graphite (FG) foil, all plotted as a function of the final heat treatment temperature.

FIG. 7 (a) Thermal conductivity values of the GO gel-derived unitary graphene layer alone (▪), unitary graphene matrix-expanded graphite reinforcement composite (♦, experimental values), expanded graphite mat alone (exfoliated graphite worms broken up into separated graphite flakes and clustered into a thin mat) and FG foil alone (▴, re-compressed worms without worm break-up and flake separation as a point of reference) plotted as a function of the final graphitization or re-graphitization temperature, along with theoretically predicted values (x, unitary graphene matrix-expanded graphite composite) based on a rule-of-mixture law (final graphitization time=1 hour for all specimens); (b) Thermal conductivity values of the GO gel-derived unitary graphene layer alone (▪), unitary graphene matrix-expanded graphite composite (♦), and polyimide-derived pyrolytic graphite (PG) plotted as a function of the final graphitization or re-graphitization temperature for one hour, along with those of PG graphitized for 3 hours.

FIG. 8 (a) Tensile strength of unitary graphene matrix material from GO gel, paper of GO platelets (not from GO gel state), and flexible graphite foil over a range of heat treatment temperatures; (b) Tensile strength and (c) Rockwell hardness values of unitary graphene matrix/CNT reinforcement composites, unitary graphene matrix/expanded graphite reinforcement composites, and unitary graphene matrix/carbon black reinforcement composites plotted as a function of the filler weight percentage, and (d) Rockwell hardness of unitary graphene matrix material only and its CNT-reinforced version plotted as a function of the heat treatment temperature.

FIG. 9 Viscosity values of graphene gel plotted as a function of viscometer spindle speed (proportional to a shear rate): (a) linear-linear scale, (b) log-linear scale, and (c) log-log scale.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides a process for producing a unitary graphene material, the process comprising:

-   (a) preparing a graphene oxide gel having graphene oxide molecules     dispersed in a fluid medium wherein the graphene oxide molecules     contain an oxygen content higher than 20% by weight (typically     higher than 30% and more typically between 30% and 46% by weight); -   (b) dispensing and depositing a layer of graphene oxide gel onto a     surface of a supporting substrate to form a deposited graphene oxide     gel thereon, wherein the dispensing and depositing procedure     includes shear-induced thinning of the graphene oxide gel (resulting     in graphene oxide molecules well-packed and well-aligned in desired     direction(s), conducive to merging and integration of GO molecules     during a subsequent heat treatment); -   (c) partially or completely removing the fluid medium from the     deposited graphene oxide gel layer to form a graphene oxide layer     having an inter-plane spacing d₀₀₂ of 0.4 nm to 1.2 nm as determined     by X-ray diffraction and an oxygen content no less than 20% by     weight; and -   (d) heat treating the graphene oxide layer to form said unitary     graphene material at a heat treatment temperature higher than     100° C. to an extent that an inter-plane spacing d₀₀₂ is decreased     to a value of from 0.3354 nm to 0.4 nm and the oxygen content is     decreased to less than 5% by weight.

In a more preferred embodiment, step (c) includes forming a graphene oxide layer having an inter-plane spacing d₀₀₂ of 0.4 nm to 0.7 nm and an oxygen content no less than 20% by weight; and step (d) includes heat-treating the graphene oxide layer to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.36 nm and the oxygen content is decreased to less than 2% by weight (most preferably between 0.001% to 0.01% by weight).

The unitary graphene material is obtained from heat-treating a graphene oxide gel at a temperature higher than 100° C. (preferably higher than 500° C., more preferably higher than 1,250° C., further preferably higher than 2,000° C., and advantageously higher than 2,500° C. if a perfect or nearly perfect graphene single crystal is desired) and contains chemically bonded graphene molecules. These planar aromatic molecules or graphene planes (hexagonal structured carbon atoms) are parallel to one another. The lateral dimensions (length or width) of these planes are huge, typically several times or even orders of magnitude larger than the maximum or “crystallite dimension (or maximum constituent graphene plane dimension) of the starting graphite particles. The presently invented unitary graphene material is a “giant graphene crystal” or “giant graphene particle” having all constituent graphene planes being essentially parallel to one another. This is a unique and new class of material that has not been previously discovered, developed, or suggested to possibly exist.

The graphene oxide gel is a very unique and novel class of material that surprisingly has great cohesion power (self-bonding, self-polymerizing, and self-crosslinking capability) and adhesive power (capable of chemically bonding to a wide variety of solid surfaces). These characteristics have not been taught or hinted in the prior art. The GO gel is obtained by immersing powders or filaments of a starting graphitic material in an oxidizing liquid medium (e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel. The starting graphitic material may be selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof.

When the starting graphite powders or filaments are mixed in the oxidizing liquid medium, the resulting slurry (heterogeneous suspension) initially appears completely dark and opaque. When the oxidation of graphite proceeds at a reaction temperature for a sufficient length of time under a controlled pH condition, the reacting mass can eventually become a homogeneous solution having no discernible or visually identifiable dispersed solid particle (as opposed to the initially heterogeneous suspension that contain identifiable solid particles). The solution can be optically translucent or transparent or brown-colored, which also looks and behaves like a polymer gel. This heavy oxidation-induced graphene oxide gel is composed of graphene oxide molecules dissolved in the liquid medium. The graphene oxide molecules, prior to any subsequent heat treatment, have an oxygen content no less than 20% by weight (typically from 40-50% by weight) and their molecular weights are typically less than 43,000 g/mole (often less than 4,000 g/mole, but typically greater than 200 g/mole) while in a gel state. The graphene oxide gel is composed of graphene oxide molecules dissolved in an acidic medium having a pH value of typically no higher than 5.

The graphene oxide gel has a typical viscosity from 500 centipoise (cP) to 500,000 cP when measured at 20° C. prior to shear-induced thinning. The viscosity is more typically greater than 2,000 cP and less than 300,000 cP when measured at 20° C. prior to the shear-induced thinning procedure. Preferably, the viscosity of the GO gel as a precursor to unitary graphene material is in the range of 2,000-50,000 cP. Preferably, the GO gel is subjected to a shear stress field that the viscosity is reduced to below 2,000 cP (or even below 1,000 cP) during or after shear-induced thinning. In an embodiment, the graphene oxide gel has a viscosity greater than 5,000 cP when measured at 20° C. prior to shear-induced thinning, but is reduced to below 5,000 cP (preferably and typically below 2,000 cP or even below 1,000 cP) during or after shear-induced thinning. The viscosity data measured at 20° C., shown in FIGS. 9( a), 9(b), and 9(c) as an example, clearly indicate that even an ultra-high viscosity value (e.g., 300,000 cP) can be reduced down to 1,000-2,000 cP with a sufficiently high shear rate. This is a reduction by more than 2 orders of magnitude, a highly unexpected observation. The straight line of the data when plotted in a log-log scale indicates a shear thinning fluid flow behavior.

In step (b), the GO gel is formed into a shape preferably under the influence of a shear stress. One example of such a shearing procedure is casting or coating a thin film of GO gel (gel-like fluid) using a coating machine. This procedure is similar to a layer of varnish, paint, coating, or ink being coated onto a solid substrate. The roller, “doctor's blade”, or wiper creates a shear stress when the film is shaped, or when a relative motion is effected between the roller/blade/wiper and the supporting substrate. Quite unexpectedly and significantly, such a shearing action reduces the effective viscosity of the GO gel and enables the planar graphene oxide (GO) molecules to well align along, for instance, a shearing direction. Further surprisingly, such a molecular alignment state or preferred orientation is not disrupted when the liquid components in the GO gel are subsequently removed to form a well-packed GO mass that is at least partially dried. The dried GO mass has a high birefringence coefficient between an in-plane direction and the normal-to-plane direction. Another example of such a procedure is injecting or die-casting a GO mass into a mold cavity or shaping die/tooling under the influence of a shearing stress. The liquid component of the sheared GO mass in a mold cavity is then partially or completely removed to obtain a partially or totally dried GO mass containing well-packed and well-aligned “live” GO molecules.

This dried GO mass is then subjected to a properly programmed heat treatment that can be divided into four distinct heat treatment temperature (HTT) regimes:

-   Regime 1 (100° C.-500° C.): In this temperature range (the thermal     reduction regime), the GO mass primarily undergoes thermally-induced     reduction reactions, leading to a reduction of oxygen content from     typically 30-50% (as dried) to 5-6%. This treatment results in a     reduction of inter-graphene spacing from approximately 0.6-1.0 nm     (as dried) to approximately 0.4 nm and an increase in in-plane     thermal conductivity from approximately 100 W/mK to 450 W/mK. Even     with such a low temperature range, some chemical linking occurs. The     GO molecules remain well-aligned, but the inter-GO spacing remains     relative large (0.4 nm or larger). Many O-containing functional     groups survive. -   Regime 2 (500° C.-1,250° C.): In this chemical linking regime,     extensive chemical combination, polymerization, and cross-linking     between adjacent GO molecules occur. The oxygen content is reduced     to typically 0.7% (<<1%), resulting in a reduction of inter-graphene     spacing to approximately 0.345 nm. This implies that some initial     graphitization has already begun at such a low temperature, in stark     contrast to conventional graphitizable materials (such as carbonized     polyimide film) that typically require a temperature as high as     2,500° C. to initiate graphitization. This is another distinct     feature of the presently invented unitary graphene material and its     production processes. These chemical linking reactions result in an     increase in in-plane thermal conductivity of a unitary graphene thin     film to 1,400-1,500 W/mK, and/or in-plane electrical conductivity to     3,000-4,000 S/cm. -   Regime 3 (1,250° C.-2,000° C.): In this ordering and     re-graphitization regime, extensive graphitization or graphene plane     merging occurs, leading to significantly improved degree of     structural ordering. As a result, the oxygen content is reduced to     typically 0.01% and the inter-graphene spacing to approximately     0.337 nm (achieving degree of graphitization from 1% to     approximately 80%, depending upon the actual HTT and length of     time). The improved degree of ordering is also reflected by an     increase in in-plane thermal conductivity to >1,680 W/mK, and/or     in-plane electrical conductivity to 5,000-7,000 S/cm. -   Regime 4 (2,000° C.-3,000° C. or higher): In this re-crystallization     and perfection regime, extensive movement and elimination of grain     boundaries and other defects occur, resulting in the formation of     perfect or nearly perfect single crystals, or poly-crystalline     graphene crystals with incomplete grain boundaries or huge grains     (these grains can be orders of magnitude larger than the original     grain sizes of the starting graphite particles for GO gel     production. The oxygen content is essentially eliminated, typically     0%-0.001%. The inter-graphene spacing is reduced to down to     approximately 0.3354 nm (degree of graphitization from 80% to nearly     100%), corresponding to that of a perfect graphite single crystal.     Quite interestingly, the graphene single crystal or poly-crystal has     all the graphene planes being closely packed and bonded and all     aligned along one direction, a perfect orientation. Such a perfectly     oriented structure has not been produced even with the HOPG being     subjected concurrently to an ultra-high temperature (3,400° C.)     under an ultra-high pressure (300 Kg/cm²). The unitary graphene     entity car achieve such a highest degree of perfection with a     significantly lower temperature and an ambient (or slightly higher     compression) pressure. The unitary graphene material thus obtained     exhibits an in-plane thermal conductivity up to slightly >1,800     W/mK, and in-plane electrical conductivity to 15,000-25,000 S/cm.     The presently invented unitary graphene material can be obtained by     heat-treating the dried GO mass with a temperature program that     covers at least the first regime (typically requiring 1-4 hours in     this temperature range if the temperature never exceeds 500° C.),     more commonly covers the first two regimes (1-2 hours preferred),     still more commonly the first three regimes (preferably 0.5-2.0     hours in Regime 3), and most commonly all the 4 regimes (Regime 4,     for 0.2 to 1 hour, may be implemented to achieve the highest     conductivity).

X-ray diffraction patterns were obtained with an X-ray diffractometer equipped with CuKcv radiation. The shift and broadening of diffraction peaks were calibrated using a silicon powder standard. The degree of graphitization, g, was calculated from the X-ray pattern using the Mering's Eq, d₀₀₂=0.3354 g+0.344 (1−g), where d₀₀₂ is the interlayer spacing of graphite or graphene crystal in nm. This equation is valid only when d₀₀₂ is equal or less than approximately 0.3440 nm. The unitary graphene material or lightly oxidized graphite crystalline material having a d₀₀₂ higher than 0.3440 nm reflects the presence of oxygen-containing functional groups (such as —OH, >0, and —COOH on graphene molecular plane surfaces) that act as a spacer to increase the inter-graphene spacing.

Another structural index that can be used to characterize the degree of ordering of the presently invented unitary graphene material and conventional graphite crystals is the “mosaic spread,” which is expressed by the full width at half maximum of a rocking curve (X-ray diffraction intensity) of the (002) or (004) reflection. This degree of ordering characterizes the graphite or graphene crystal size (or grain size), amounts of grain boundaries and other defects, and the degree of preferred grain orientation. A nearly perfect single crystal of graphite is characterized by having a mosaic spread value of 0.2-0.4. Most of our unitary graphene materials have a mosaic spread value in this range of 0.2-0.4 (with a heat treatment temperature no less than 2,000° C.). However, some values are in the range of 0.4-0.7 if the highest heat treatment temperature (TTT) is between 1,250 and 2,000° C., and in the range of 0.7-1.0 if the TTT is between 500 and 1,250° C.

The present invention provides a process for producing a unitary graphene material or a unitary graphene matrix composite composed of a unitary graphene as a matrix material (the continuous phase) and CNT or carbon fibers as a discrete filler phase. In one preferred embodiment, the unitary graphene matrix composite is composed of: (a) a unitary graphene matrix containing closely packed and chemically bonded graphene planes (preferably having an inter-graphene plane spacing of 0.3354 to 0.40 nm and, optionally, an oxygen content of 0.001% to 10% by weight), which unitary graphene matrix is obtained from heat-treating a graphene oxide gel at a temperature higher than 100° C.; and (b) A filler or reinforcement phase (e.g. particles or filaments of carbon, graphite, metal, glass, ceramic, and/or polymer).

Preferably, the reinforcement phase contains a carbon or graphite filler phase selected from a carbon or graphite fiber, carbon or graphite nano-fiber, carbon nano-tube, carbon nano-rod, meso-phase carbon particle, meso-carbon micro-bead, exfoliated graphite flake with a thickness greater than 100 nm, exfoliated graphite or graphite worm, coke particle, needle coke, carbon black or acetylene black particle, activated carbon particle, or a combination thereof. The reinforcement phase occupies a weight fraction of 0.01% to 99% (preferably 10% to 70%) based on the total composite weight. The carbon or graphite filler phase is preferably in a particulate, filamentary, or rod-like form dispersed in the unitary graphene matrix. These discrete particles, filaments, and cylindrical shape fillers are the dispersed phase (reinforcement or filler phase) and the GO-derived unitary graphene material is the continuous phase (matrix). Preferably and typically, most of the chemically bonded graphene planes in the unitary graphene matrix are parallel to one another. Typically, the carbon or graphite filler is chemically bonded by the unitary graphene matrix material. This chemical bonding is more pronounced if the carbon/graphite filler is chemically treated (e.g. using a mixture of sulfuric acid and nitric acid) prior to being mixed with the GO gel.

The heat treatment temperature conditions for GO are such that the unitary graphene material or the unitary graphene matrix composite is relatively pore-free having a physical density of at least 1.5 g/cm³ or a porosity level lower than 20%. Under more typical processing conditions, the unitary graphene or the unitary graphene matrix composite has a physical density of at least 1.7 g/cm³ or a porosity level lower than 10%. In most cases, the unitary graphene or the unitary graphene matrix composite has a physical density greater than 1.8 g/cm³ or a porosity level less than 5%. The chemically bonded graphene planes in the unitary graphene or graphene matrix composite typically contain a combination of sp² and sp³ electronic configurations (particularly for those unitary graphene materials prepared with the maximum treatment temperature lower than 2,000° C.).

In a preferred embodiment of the present invention, the process for producing the unitary graphene matrix composite comprises: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium to form a homogeneous solution, wherein the graphene oxide gel is optically transparent, translucent, or brown colored; (b) mixing the carbon or graphite filler phase in the graphene oxide gel to form a slurry; (c) dispensing the slurry into a cavity of a molding tool or forming the slurry into a desired shape under the influence of a shear stress (to create shear-induced thinning and molecular orientation); (d) partially or completely removing the fluid medium from the slurry to form a composite precursor; and (e) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. (preferably >500° C., more preferably >1,250° C., or even >2,000° C.). Although not required, higher temperatures may be used if so desired.

In this process, steps (c) and (d) preferably include feeding a sheet of a solid substrate material from a roller to a deposition zone, dispensing the slurry or suspension onto a surface of the sheet of solid substrate material to form a slurry layer thereon, shearing/compressing and drying the slurry or suspension to form a dried composite precursor layer deposited on the substrate surface, and collecting composite precursor-deposited substrate sheet on a collector roller. The process may further comprise a step of further compressing the composite precursor prior to being collected on the collector roller. This makes a roll-to-roll process amenable to mass production of graphene matrix composites.

Alternatively, the process may comprise: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium to form a homogeneous solution; (b) forming the carbon or graphite filler phase into a desired porous shape (e.g. finned heat sink-like shape) having pores therein, and impregnating the graphene oxide gel into these pores of the desired porous shape to form an impregnated shape under the influence of a shear stress; (c) partially or completely removing the fluid medium from the impregnated shape to form a composite precursor; and (d) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. Again, the re-graphitization temperature is preferably >500° C. and more preferably >1,250° C. Although not required, higher heat treatment temperatures may be used if so desired. The desired porous shape may be a porous woven fabric, porous non-woven fabric, porous mat, or porous paper.

In yet another preferred embodiment, the process for producing the unitary graphene matrix composite comprises: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium; (b) combining the carbon or graphite filler phase and the graphene oxide gel to form a graphene oxide gel-impregnated shape of fiber yarns or bundles (e.g. in a finned heat sink shape) wherein the action of combining or impregnating is conducted under a shear stress; (c) partially or completely removing the fluid medium from graphene oxide gel-impregnated shape to form a composite precursor; and (d) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. The graphene oxide gel-impregnated shape may be selected from a unidirectional, bi-directional, multi-directional, angle-plied, woven, or filament-wound shape.

We have surprisingly observed that the processes for producing conventional resin matrix composites, such as filament winding, pultrusion, and pre-impregnating, may be adapted to fabricate the graphene matrix composite. The winding, pultrusion, and impregnation can produce a shear stress field that induces shear thinning and molecular orientations of the nearby GO molecules. This preferred orientation is also preserved and even enhanced when the resulting GO matrix composite is dried and heat-treated.

This is quite surprising for several reasons: (1) The GO gel and conventional polymer melts or polymer-solvent solutions appear to exhibit very different and distinct rheological behaviors; (2) It is well-known in the field of polymer science that highly aromatic chains are typically not soluble, melt-able, or flowable to enable solution or melt processing and GO molecules are highly aromatic; (3) Much to the surprise of polymer scientists, heavy oxidation can chemically convert discrete solid graphite flakes to soluble GO molecules and these highly aromatic molecules can be chemically linked together to form huge 2D giant molecules or 3D network of “cross-linked” graphene chains that provide cohesiveness and adhesiveness required of a resin matrix composite having a good resin-filler interfacial bonding.

The graphene oxide gel may be prepared by immersing a graphitic material in a powder or fibrous form in an oxidizing liquid to form an initially optically opaque suspension in a reaction vessel at a reaction temperature for a length of time sufficient to obtain a graphene oxide gel that is optically transparent or translucent. The graphene oxide gel is composed of graphene oxide molecules dispersed in an acidic medium having a typical pH value of no higher than 5 and the graphene oxide molecules have an oxygen content typically no less than 20% by weight when the system is in a gel state.

Specifically, a graphitic material may be immersed in an oxidizing agent to form an optically opaque suspension. It is initially opaque because the starting graphitic material is in a carbon or graphite particulate form having a particle size or chemical nature that scatters visible wavelength or absorbs light. Useful starting materials include natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof. As the oxidizing reaction proceeds to a critical extent, an optically transparent or translucent solution is formed.

All the aforementioned processes may further comprise a step of compressing the composite precursor prior to or during heat treating. Preferably, the processing conditions involve a shear stress field that promotes alignment and/or packing of GO molecules.

The graphene oxide (GO) gel-derived unitary graphene material and the unitary graphene matrix composite have the following characteristics (separately or in combination):

-   (1) The unitary graphene matrix material, alone or with a filler     phase, is an integrated graphene phase that is either a graphene     single crystal or a poly-crystal having multiple grains with     incomplete grain boundaries. When made into a thin film (e.g. <200     μm) or formed under a desired shearing stress field condition, both     the unitary graphene matrix alone or the corresponding graphene     matrix composite have wide/long chemically bonded graphene planes     that are essentially oriented parallel to one another. In other     words, the crystallographic c-axis directions of all grains and all     their constituent graphene planes are essentially pointing in the     same direction. It may be noted that the grains in a graphene     poly-crystal have very poorly delineated or incomplete grain     boundaries. These grains are essentially a single grain with some     residual demarcation lines (e.g., FIG. 3( f)). Such type of graphene     poly-crystal is best described as a graphene single crystal with     some aligned but sporadic defects. These defects can be eliminated     to form a practically perfect single crystal if the unitary graphene     structure is allowed to undergo re-crystallization at a temperature     higher than approximately 2,500° C. for a sufficient length of time.     This conclusion was drawn after an extensive investigation using a     combination of SEM, TEM, selected area diffraction (with a TEM),     X-ray diffraction, atomic force microscopy (AFM), Raman     spectroscopy, and FTIR. -   (2) The paper-like sheets of exfoliated graphite worms (i.e.,     flexible graphite foils), mats of expanded graphite flakes (100 nm     in thickness), and paper or membrane of graphene or GO platelets are     a simple, un-bonded aggregate/stack of multiple discrete graphite     flakes or discrete platelets of graphene, GO, or RGO. In contrast,     the unitary graphene matrix of the present invention is a fully     integrated, single graphene entity or monolith containing no     discrete flakes or platelets derived from the GO gel. -   (3) In prior art processes, discrete graphene sheets (<<100 nm) or     expanded graphite flakes (>100 nm) that constitute the original     structure of graphite particles could be obtained via expanding,     exfoliating, and separating treatments. By simply mixing and     re-compressing these discrete sheets/flakes into a thin film, one     could attempt to orient these sheets/flakes hopefully along one     direction. However, with these conventional processes, the     constituent flakes or sheets of the resulting film (aggregate,     paper, membrane, or mat) would remain as discrete     flakes/sheets/platelets that can be easily discerned or clearly     observed even with an un-assisted eye or under a low-magnification     optical microscope (×100-×1000).

In contrast, the preparation of the presently invented unitary graphene structure involves heavily oxidizing the original graphite particles, to the extent that practically every one of the original graphene planes has been oxidized and isolated from one another to become individual molecules that possess highly reactive functional groups (e.g. —OH, >0, and —COOH) at the edge and, mostly, on graphene planes as well. These individual hydrocarbon molecules (containing elements such as O and H, in addition to carbon atoms) are dissolved in the reaction medium (e.g. mixture of water and acids) to form a gel-like mass, herein referred to as the GO gel. This gel is then cast onto a smooth substrate surface or injected into a mold cavity, typically under shear stress field conditions, and the liquid components are then removed to form a dried GO layer. When heated, these highly reactive molecules react and chemically join with one another mostly in lateral directions along graphene planes (in an edge-to-edge manner) and, in some cases, between graphene planes as well. Illustrated in FIG. 3( g) is a plausible chemical linking mechanism where only 2 aligned GO molecules are shown as an example, although a large number of GO molecules can be chemically linked together to form a unitary graphene layer. Further, chemical linking could also occur face-to-face, not just edge-to-edge. These linking and merging reactions proceed in such a manner that the molecules are chemically merged, linked, and integrated into one single entity or monolith. The molecules completely lose their own original identity and they no longer are discrete sheets/platelets/flakes. There is only one single layer-like structure (unitary graphene entity) that is one huge molecule or just a network of interconnected giant molecules with an essentially infinite molecular weight. This may also be described as a graphene single crystal (with only one grain in the entire structure or entity, or a poly-crystal (with several grains, but typically no discernible, well-defined grain boundaries). All the constituent graphene planes are very large in lateral dimensions (length and width) and, if produced under shear stress conditions (particularly into thin films, <200 μm in thickness) and heat-treated at a higher temperature (e.g. >1,250° C. or much higher), these graphene planes are essentially parallel to one another.

In-depth studies using a combination of SEM, TEM, selected area diffraction, X-ray diffraction, AFM, Raman spectroscopy, and FTIR indicate that the graphene monolith is composed of several huge graphene planes (with length/width typically >>100 μm, more typically >>1 mm, and most typically >>1 cm). These giant graphene planes are stacked and bonded along the thickness direction (crystallographic c-axis direction) often through not just the van der Waals forces (as in conventional graphite crystallites), but also covalent bonds, Not to be limited by theory, but Raman and FTIR spectroscopy studies appear to indicate the co-existence of sp² (dominating) and sp³ (weak but existing) electronic configurations, not just the conventional sp² in graphite.

-   (4) This integrated graphene entity is not made by gluing or bonding     discrete flakes/platelets together with a resin binder, linker, or     adhesive. Instead, GO molecules in the GO gel are merged through     joining or forming of covalent bonds with one another, into an     integrated graphene entity, without using any externally added     linker or binder molecules or polymers. -   (5) This unitary or monolithic graphene entity is a single crystal     (e.g. FIG. 3( e)) or poly-crystal (having incomplete grain     boundaries, FIG. 3( f)), typically with the crystallographic c-axis     in all grains being essentially parallel to each other. This entity     is derived from a GO gel, which is in turn obtained from natural     graphite or artificial graphite particles originally having multiple     graphite crystallites. Prior to being chemically oxidized, these     starting graphite crystallites have an initial length (L_(a) in the     crystallographic a-axis direction), initial width (L_(b) in the     b-axis direction), and thickness (L_(c) in the c-axis direction).     Upon heavy oxidation, these initially discrete graphite particles     are chemically transformed into highly aromatic graphene oxide     molecules having a significant concentration of edge- or     surface-borne functional groups (e.g. —OH, —COOH, etc.). These     aromatic GO molecules in the GO gel have lost their original     identity of being part of a graphite particle or flake. Upon removal     of the liquid component from the GO gel, the resulting GO molecules     form an essentially amorphous structure. Upon heat treatment     (re-graphitization treatment), these GO molecules are chemically     merged and linked into a unitary or monolithic graphene entity that     is highly ordered (essentially a single crystal when the temperature     is sufficiently high).

The resulting unitary graphene entity typically has a length or width significantly greater than the L_(a) and L_(b) of the original crystallites. The length/width of this unitary graphene entity or that of a graphene single crystal is typically greater than the L_(a) and L_(b) of the original crystallites. Even the individual grains in a poly-crystalline unitary graphene entity have a length or width significantly greater than the L_(a) and L_(b) of the original crystallites. They can be as large as the length or width of the unitary graphene entity itself, not just 2 or 3 times higher than the initial L_(a) and L_(b) of the original crystallites.

-   (6) Due to these unique chemical composition (including oxygen     content), morphology, crystal structure (including inter-graphene     spacing), and structural features (e.g. defects, incomplete or lack     of grain boundaries, chemical bonding and no gap between graphene     sheets, and no interruptions in graphene planes), the graphene oxide     gel-derived unitary or monolithic graphene layer has a unique     combination of outstanding thermal conductivity, electrical     conductivity, mechanical strength, and scratch resistance (including     elimination of the tendency for surface graphite flakes or particles     to “flake off” since there is essentially no GO gel-derived discrete     flake or platelet in this graphene monolith structure). Even in a     unitary graphene matrix composite containing expanded graphite     flakes, these flakes are essentially embraced and bonded with an     integrated graphene film, allowing no exposed flakes.

The aforementioned features are further described and explained in detail as follows: As illustrated in FIG. 1( b), a graphite particle (e.g. 100) is typically composed of multiple graphite crystallites or grains. A graphite crystallite is made up of layer planes of hexagonal networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another in a particular crystallite. These layers of hexagonal-structured carbon atoms, commonly referred to as graphene layers or basal planes, are weakly bonded together in their thickness direction (crystallographic c-axis direction) by weak van der Waals forces and groups of these graphene layers are arranged in crystallites. The graphite crystallite structure is usually characterized in terms of two axes or directions: the c-axis direction and the a-axis (or b-axis) direction. The c-axis is the direction perpendicular to the basal planes. The a- or b-axes are the directions parallel to the basal planes (perpendicular to the c-axis direction).

A highly ordered graphite particle can consist of crystallites of a considerable size, having a length of L_(a) along the crystallographic a-axis direction, a width of L_(b) along the crystallographic b-axis direction, and a thickness L, along the crystallographic c-axis direction. The constituent graphene planes of a crystallite are highly aligned or oriented with respect to each other and, hence, these anisotropic structures give rise to many properties that are highly directional. For instance, the thermal and electrical conductivity of a crystallite are of great magnitude along the plane directions (a- or b-axis directions), but relatively low in the perpendicular direction (c-axis). As illustrated in the upper-left portion of FIG. 1( b), different crystallites in a graphite particle are typically oriented in different directions and, hence, a particular property of a multi-crystallite graphite particle is the directional average value of all the constituent crystallites.

Due to the weak van der Waals forces holding the parallel graphene layers, natural graphite can be treated so that the spacing between the graphene layers can be appreciably opened up so as to provide a marked expansion in the c-axis direction, and thus form an expanded graphite structure in which the laminar character of the carbon layers is substantially retained. The process for manufacturing flexible graphite is well-known and the typical practice is described in U.S. Pat. No. 3,404,061 to Shane et al., the disclosure of which is incorporated herein by reference. In general, flakes of natural graphite (e.g. 100 in FIG. 1( b)) are intercalated in an acid solution to produce graphite intercalation compounds (GICs, 102). The GICs are washed, dried, and then exfoliated by exposure to a high temperature for a short period of time. This causes the flakes to expand or exfoliate in the c-axis direction of the graphite up to 80-300 times of their original dimensions. The exfoliated graphite flakes are vermiform in appearance and, hence, are commonly referred to as worms 104. These worms of graphite flakes which have been greatly expanded can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, foils, mats or the like (typically referred to as “flexible graphite” 106) having a typical density of about 0.04-2.0 g/cm³ for most applications.

The upper left portion of FIG. 1( a) shows a flow chart that illustrates the prior art processes used to fabricate flexible graphite foils and the resin-impregnated flexible graphite composite. The processes typically begin with intercalating graphite particles 20 (e.g., natural graphite or synthetic graphite) with an intercalant (typically a strong acid or acid mixture) to obtain a graphite intercalation compound 22 (GIC). After rinsing in water to remove excess acid, the GIC becomes “expandable graphite.” The GIC or expandable graphite is then exposed to a high temperature environment (e.g., in a tube furnace preset at a temperature in the range of 800-1,050° C.) for a short duration of time (typically from 15 seconds to 2 minutes). This thermal treatment allows the graphite to expand in its c-axis direction by a factor of 30 to several hundreds to obtain a worm-like vermicular structure 24 (graphite worm), which contains exfoliated, but un-separated graphite flakes with large pores interposed between these interconnected flakes. An example of graphite worms is presented in FIG. 2( a).

In one prior art process, the exfoliated graphite (or mass of graphite worms) is re-compressed by using a calendering or roll-pressing technique to obtain flexible graphite foils (26 in FIG. 1( a) or 106 in FIG. 1( b)), which are typically much thicker than 100 μm. An SEM image of a cross-section of a flexible graphite foil is presented in FIG. 2( b), which shows many graphite flakes with orientations not parallel to the flexible graphite foil surface and there are many defects and imperfections.

Largely due to these mis-orientations of graphite flakes and the presence of defects, commercially available flexible graphite foils normally have an in-plane electrical conductivity of 1,000-3,000 S/cm, through-plane (thickness-direction or Z-direction) electrical conductivity of 15-30 S/cm, in-plane thermal conductivity of 140-300 W/mK, and through-plane thermal conductivity of approximately 10-30 W/mK. These defects and mis-orientations are also responsible for the low mechanical strength (e.g. defects are potential stress concentration sites where cracks are preferentially initiated). These properties are inadequate for many thermal management applications and the present invention is made to address these issues.

In another prior art process, the exfoliated graphite worm 24 may be impregnated with a resin and then compressed and cured to form a flexible graphite composite 28, which is normally of low strength as well. In addition, upon resin impregnation, the electrical and thermal conductivity of the graphite worms could be reduced by two orders of magnitude.

Alternatively, the exfoliated graphite may be subjected to high-intensity mechanical shearing/separation treatments using a high-intensity air jet mill, high-intensity ball mill, or ultrasonic device to produce separated nano graphene platelets 33 (NGPs) with all the graphene platelets thinner than 100 nm, mostly thinner than 10 nm, and, in many cases, being single-layer graphene (also illustrated as 112 in FIG. 1( b). An NGP is composed of a graphene sheet or a plurality of graphene sheets with each sheet being a two-dimensional, hexagonal structure of carbon atoms.

Further alternatively, with a low-intensity shearing, graphite worms tend to be separated into the so-called expanded graphite flakes (108 in FIG. 1( b) having a thickness >100 nm. These flakes can be formed into graphite paper or mat 106 using a paper- or mat-making process. This expanded graphite paper or mat 106 is just a simple aggregate or stack of discrete flakes having defects, interruptions, and mis-orientations between these discrete flakes.

For the purpose of defining the geometry and orientation of an NGP, the NGP is described as having a length (the largest dimension), a width (the second largest dimension), and a thickness. The thickness is the smallest dimension, which is no greater than 100 nm, preferably smaller than 10 nm in the present application. When the platelet is approximately circular in shape, the length and width are referred to as diameter. In the presently defined NGPs, both the length and width can be smaller than 1 μm, but can be larger than 200 μm.

A mass of multiple NGPs (including discrete sheets/platelets of single-layer and/or few-layer graphene, 33 in FIG. 1( a)) may be made into a graphene film/paper (34 in FIG. 1( a) or 114 in FIG. 1( b)) using a film- or paper-making process. FIG. 3( b) shows a SEM image of a cross-section of a graphene paper/film prepared from discrete graphene sheets using a paper-making process. The image shows the presence of many discrete graphene sheets being folded or interrupted (not integrated), most of platelet orientations being not parallel to the film/paper surface, the existence of many defects or imperfections. NGP aggregates, even when being closely packed, exhibit a thermal conductivity higher than 1,000 W/mK only when the film or paper is cast and strongly pressed into a sheet having a thickness lower than 10 μm. A heat spreader in many electronic devices or a fin member in a heat sink is normally required to be thicker than 25 μm and, more desirably, thicker than 50 μm based mainly on handling ease and structural integrity considerations (but no greater than 200 μm due to device volume constraint).

The precursor to the unitary graphene layer is graphene oxide gel 21 (FIG. 1( a)). This GO gel is obtained by immersing a graphitic material 20 in a powder or fibrous form in a strong oxidizing liquid in a reaction vessel to form a suspension or slurry, which initially is optically opaque and dark. This optical opacity reflects the fact that, at the outset of the oxidizing reaction, the discrete graphite flakes and, at a later stage, the discrete graphene oxide flakes scatter and/or absorb visible wavelengths, resulting in an opaque and generally dark fluid mass. If the reaction between graphite powder and the oxidizing agent is allowed to proceed at a sufficiently high reaction temperature for a sufficient length of time, this opaque suspension is transformed into a brown-colored and typically translucent or transparent solution, which is now a homogeneous fluid called “graphene oxide gel” (21 in FIG. 1( a)) that contains no discernible discrete graphite flakes or graphite oxide platelets. If dispensed and deposited under a shear stress field, the GO gel undergoes viscosity reduction and molecular orientation to form “oriented GO” 35, which can be heat-treated to become a unitary graphene material 37.

Again, this graphene oxide gel is typically optically transparent or translucent and visually homogeneous with no discernible discrete flakes/platelets of graphite, graphene, or graphene oxide dispersed therein. In the GO gel, the GO molecules are uniformly dissolved in an acidic liquid medium. In contrast, conventional suspension of discrete graphene sheets, graphene oxide sheets, and expanded graphite flakes in a fluid (e.g. water, organic acid or solvent) look dark, black or heavy brown in color with individual graphene or graphene oxide sheets or expanded graphite flakes discernible or recognizable even with naked eyes or a low-magnification light microscope (100×-1,000×).

The graphene oxide molecules dissolved in the liquid medium of a graphene oxide gel are aromatic chains that have an average number of benzene rings in the chain typically less than 1,000, more typically less than 500, and many less than 100. Most of the molecules have more than 5 or 6 benzene rings (mostly >10 benzene rings) from combined atomic force microscopy, high-resolution TEM, and molecular weight measurements. Based on our elemental analysis, these benzene-ring type of aromatic molecules are heavily oxidized, containing a high concentration of functional groups, such as —COOH and —OH and, therefore, are “soluble” (not just dispersible) in polar solvents, such as water. The estimated molecular weight of these graphene oxide polymers in the gel state is typically between 200 g/mole and 43,000 g/mole, more typically between 400 g/mole and 21,500 g/mole, and most typically between 400 g/mole and 4,000 g/mole.

These soluble molecules behave like polymers and are surprisingly capable of reacting and getting chemically connected with one another (during the subsequent heat treatment or re-graphitization treatment) to form a unitary graphene layer of good structural integrity and high thermal conductivity. Conventional discrete graphene sheets, graphene oxide sheets, or graphite flakes do not have any self-reacting or cohesive bonding capability. Also very surprisingly, during the subsequent heat treatment or re-graphitization treatment, these soluble molecules in the GO gel are capable of chemically bonding a carbon or graphite filler phase (e.g. carbon fibers, expanded graphite flakes, CNTs, carbon black particles, etc.) dispersed in the GO gel.

Again, specifically and most significantly, these graphene oxide molecules present in a GO gel state are capable of chemically bonding, linking, or merging with one another and getting integrated into extremely long and wide graphene layers (e.g. FIG. 3( a)) when the gel is dried and heat-treated at a sufficiently high temperature for a sufficiently long period of time. These graphene layers can run as wide as the specimen width itself (up to hundreds of centimeters) that are parallel to one another. No individual graphene platelets or sheets are discernible; they have been chemically converted to chemically active or live GO molecules that are fully linked and integrated chemically with one another to form a layer-like unitary body in the graphene plane direction and these unitary bodies appear to be chemically bonded with one another along the thickness-direction (or Z-direction). X-ray diffraction studies have confirmed that the d-spacing (inter-graphene plane distance) has been recovered back to approximately 0.3354 nm (with 0%-0.001% by weight of oxygen) to 0.40 nm (with approximately 5.0-10% oxygen). There does not appear to be any gap between these graphene layers and, hence, these layers have been essentially merged into one big unitary body, which is a graphene single crystal. FIG. 3( a) depicts an example of such a huge unitary body. Although there appears to be some demarcations between unitary layers, these perceived demarcations are due to slightly different widths between layers. Each layer is composed of one of multiple graphene planes parallel to one another. These seemingly individual unitary layers actually have formed into a single integrated entity or a graphene single crystal. The formation process for such a graphene single crystal is further illustrated in FIG. 3( c).

It may be noted that the presently invented graphene single crystal is fundamentally different and patently distinct from the catalytic CVD graphene thin film in terms of chemical composition, micro-structure, morphology, process of production, all chemical and physical properties, and intended applications. This is explained as follows:

-   (a) As schematically shown in FIG. 3( d), the prior art graphene     poly-crystal obtained by CVD of hydrocarbon on a catalytic surface     (e.g. Cu or Ni) is typically composed of many grains with grain size     typically smaller than 10 μm (most often <5 μm). These grains also     have different orientations with respect to one another. The CVD     graphene contains many defects, e.g., grain boundaries, line     defects, vacancies, and other lattice defects, such as those many     carbon atoms configured in pentagons, heptagons, or octagons, as     opposed to the normal hexagon. These defects impede the flow of     electrons and phonons. -   (b) In contrast, FIG. 3( e) shows a schematic of a graphene single     crystal of the present invention having just one single grain or     domain. There are no grain boundaries that can impede the movement     of electrons or phonons and, hence, this single-grain single-crystal     material has an exceptionally high electrical conductivity and     thermal conductivity. -   (c) FIG. 3( f) shows a schematic of another graphene single crystal     of the present invention, which is a “poly-crystal” with incomplete     grain boundaries. The graphene planes in all the grains are oriented     parallel to one another. -   (d) The presently invented graphene single crystal from GO gel can     have some oxygen content, but no hydrogen (H). In contrast, the     catalytic CVD graphene film inherently has some hydrogen or     nitrogen, but no oxygen. -   (e) Typically, the CVD graphene film grown on Cu or Ni surface is     single layer or inhomogeneous few-layer graphene with a thickness     less than 2 nm (the underlying Cu or Ni foil is not capable of     providing catalytic effect when the deposited carbon layer exceeds 2     nm). These ultra-thin layers are thus optically transparent and are     intended to replace the ITO glass for use in touch panel screens.     These ultra-thin films are not rigid enough to easily handled and     implemented as a heat spreader in a smart phone. In contrast, our     graphene monolith is typically thicker than 10 nm (more typically     thicker than 100 nm and most typically thicker than 10 μm) and,     hence, is optically opaque. The graphene monolith of the present     invention has a significantly higher thermal conductivity and can be     more easily handled when being implemented into an electronic device     (e.g. a mobile phone) as a heat spreader, or made into a finned heat     sink for a LED lighting device. -   (f) The electrical conductivity (<1,000 S/cm) and thermal     conductivity (<500 W/mK) of the CVD graphene films are typically     significantly lower than those of the presently invented graphene     single crystals even though these CVD films are typically thinner     than 2 nm and our graphene single crystals are typically thicker     than 10 nm (often thicker than 10 μm).

The starting graphitic material to be heavily oxidized for the purpose of forming graphene oxide gel may be selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof. The graphitic material is preferably in a powder or short filament form having a dimension lower than 20 μm, more preferably lower than 10 μm, further preferably smaller than 5 μm, and most preferably smaller than 1 μM.

Using artificial graphite with an average particle size of 9.7 μm as an example, a typical procedure involves dispersing graphite particles in an oxidizer mixture of sulfuric acid, nitric acid, and potassium permanganate (at a weight ratio of 3:1:0.05) at a temperature of typically 0-60° C. for typically at least 3 days, preferably 5 days, and more preferably 7 days or longer. The average molecular weight of the resulting graphene oxide molecules in a gel is approximately 20,000-40,000 g/mole if the treatment time is 3 days, <10,000 g/mole if 5 days, and <4,000 g/mole if longer than 7 days. The required gel formation time is dependent upon the particle size of the original graphitic material, a smaller size requiring a shorter time. It is of fundamental significance to note that if the critical gel formation time is not reached, the suspension of graphite powder and oxidizer (graphite particles dispersed in the oxidizer liquid) appears completely opaque and heterogeneous, meaning that discrete graphite particles or flakes remain suspended (but not dissolved) in the liquid medium. As soon as this critical time is exceeded, the whole suspension becomes optically translucent or transparent (if sufficiently low GO contents) and brown colored, meaning that the heavily oxidized graphite completely loses its original graphite identity and the resulting graphene oxide molecules are completely dissolved in the oxidizer liquid, forming a homogeneous solution (no longer just a suspension or slurry).

It must be further noted that if the suspension or slurry, with a treatment time being shorter than the required gel formation time, is rinsed and dried, we would simply recover a graphite oxide powder or graphite intercalation compound (GIC) powder, which can be exfoliated and separated to produce discrete nano graphene platelets (NGPs). Without an adequate amount of a strong oxidizing agent and an adequate duration of oxidation time, the graphite or graphite oxide particles would not be converted into the GO gel state.

The graphene oxide-derived unitary graphene matrix composite containing a carbon or graphite filler phase of the present invention typically has a thermal conductivity greater than 800 W/mK, more typically greater than 1,000 W/mK (even when the film thickness is greater than 10 μm) and often greater than 1,700 W/mK. This latter valve is typically obtained when the carbon/graphite filler is exfoliated graphite flakes (>100 nm, but preferably <500 nm) or pristine graphene platelets (<100 nm, preferably <10 nm) and when the final heat treatment temperature is higher than 2,500° C. The graphene matrix composite typically has an electrical conductivity greater than 3,000 S/cm (even >10,000 S/cm). This high electrical conductivity (greater than 3000 S/cm and up to 15,000 S/cm) can be achieved concurrently with a thermal conductivity greater than 1,000 W/mK (up to 1,800 W/mK). Quite often, the unitary graphene matrix composite can exhibit a combination of a high electrical conductivity (greater than 1,500 S/cm, more often >3,000 S/cm), a high thermal conductivity (greater than 600 W/mK, more often greater than 800 W/mK), a relatively high physical density (greater than 1.8 g/cm³), and a relatively high tensile strength (greater than 40 MPa, often >80 MPa, and can be >120 MPa). Unidirectional carbon fiber reinforced graphene matrix composites can exhibit a tensile strength significantly higher than 200 MPa. The unitary graphene matrix composite also exhibits an exceptional surface hardness and scratch resistance, eliminating the tendency to flake off (to emit free carbon or graphite particles into air) which has been a serious problem associated with the flexible graphite foil and the recompressed graphene platelet foil.

If he graphene oxide gel is obtained from a graphitic material having an original graphite grain size (e.g. an average grain size, D_(g)), the resulting unitary graphene material is a single crystal or a poly-crystal graphene structure having a grain size significantly larger than this original grain size. The unitary graphene material does not have any grain that can be identified to be associated with any particular particle of the starting graphitic material. Original particles have already completely lost their identity when they are converted into graphite oxide molecules that are chemically linked up and merged or integrated into a network of graphene chains essentially infinite in molecular weight.

Further, even if graphene oxide gel is obtained from a graphitic material having multiple graphite crystallites exhibiting no preferred crystalline orientation (e.g. powder of natural graphite) as determined by an X-ray diffraction or electron diffraction method, the resulting unitary graphene material (a single crystal or a poly-crystal graphene structure) typically exhibits a very high degree of preferred crystalline orientation as determined by the same X-ray diffraction or electron diffraction method. This is yet another piece of evidence to indicate that the constituent graphene planes of hexagonal carbon atoms that constitute the particles of the original or starting graphitic material have been chemically modified, converted, re-arranged, re-oriented, linked or cross-linked, merged and integrated, re-graphitized, and even re-crystallized.

EXAMPLE 1 Preparation of Discrete Nano Graphene Platelets (NGPs) and Expanded Graphite Flakes

Chopped graphite fibers with an average diameter of 12 μm and natural graphite particles were separately used as a starting material, which was immersed in a mixture of concentrated sulfuric acid, nitric acid, and potassium permanganate (as the chemical intercalate and oxidizer) to prepare graphite intercalation compounds (GICs). The starting material was first dried in a vacuum oven for 24 h at 80° C. Then, a mixture of concentrated sulfuric acid, fuming nitric acid, and potassium permanganate (at a weight ratio of 4:1:0.05) was slowly added, under appropriate cooling and stirring, to a three-neck flask containing fiber segments. After 16 hours of reaction, the acid-treated graphite fibers or natural graphite particles were filtered and washed thoroughly with deionized water until the pH level of the solution reached 6. After being dried at 100° C. overnight, the resulting graphite intercalation compound (GIC) was subjected to a thermal shock at 1050° C. for 45 seconds in a tube furnace to form exfoliated graphite (or graphite worms).

Five grams of the resulting exfoliated graphite (graphite worms) were mixed with 2,000 ml alcohol solution consisting of alcohol and distilled water with a ratio of 65:35 for 12 hours to obtain a suspension. Then the mixture or suspension was subjected to ultrasonic irradiation with a power of 200 W for various times. After two hours of sonication, EG particles were effectively fragmented into thin NGPs. The suspension was then filtered and dried at 80° C. to remove residue solvents. The as-prepared NGPs have an average thickness of approximately 9.7 nm.

Another five grams of the resulting exfoliated graphite (EG) were subjected to low-intensity air jet milling to break up graphite worms, forming expanded graphite flakes (having an average thickness of 139 nm).

EXAMPLE 2 Preparation of Single-Layer Graphene Sheets from Meso-Carbon Micro-Beads MCMBs

Meso-carbon microbeads (MCMBs) were supplied from China Steel Chemical Co. This material has a density of about 2.24 g/cm³ with a median particle size of about 16 μm. MCMB (10 grams) were intercalated with an acid solution (sulfuric acid, nitric acid, and potassium permanganate at a ratio of 4:1:0.05) for 72 hours. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The intercalated MCMBs were repeatedly washed in a 5% solution of HCl to remove most of the sulphate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was neutral. The slurry was dried and stored in a vacuum oven at 60° C. for 24 hours. The dried powder sample was placed in a quartz tube and inserted into a horizontal tube furnace pre-set at a desired temperature, 1,080° C. for 45 seconds to obtain a graphene material. TEM and atomic force microscopic studies indicate that most of the NGPs were single-layer graphene.

EXAMPLE 3 Preparation of Pristine Graphene Sheets/Platelets

In a typical procedure, five grams of graphite flakes, ground to approximately 20 μm or less in sizes, were dispersed in 1,000 mL of deionized water (containing 0.1% by weight of a dispersing agent, Zonyl® FSO from DuPont) to obtain a suspension. An ultrasonic energy level of 85 W (Branson S450 Ultrasonicator) was used for exfoliation, separation, and size reduction of graphene sheets for a period of 15 minutes to 2 hours.

EXAMPLE 4 Preparation of Graphene Oxide (GO) Gel

Graphite oxide gel was prepared by oxidation of graphite flakes with an oxidizer liquid consisting of sulfuric acid, sodium nitrate, and potassium permanganate at a ratio of 4:1:0.05 at 30° C. When natural graphite flakes (particle sizes of 14 μm) were immersed and dispersed in the oxidizer mixture liquid, the suspension or slurry appears optically opaque and dark. The suspension remains opaque during the first 52 hours of reaction. However, the suspension gradually turns optically translucent (a little cloudy) when the reaction time exceeds 52 hours, and the color of the suspension changes from black to dark brown. After 96 hours, the suspension suddenly becomes an optically transparent solution with light brown color. The solution appears very uniform in color and transparency, indicating the absence of any dispersed discrete objects. The whole solution behaves like a gel, very similar to a typical polymer gel.

Surprisingly, by casting this gel on a glass surface and removing the liquid medium from the cast film we obtain a thin film of graphene oxide that is optically transparent. This thin film looks like, feels like, and behaves like a regular polymer film. However, upon re-graphitization at a temperature (typically >100° C., more typically >500° C., further typically >1,250° C., and can be >2,500° C.) for typically 1-3 hours, this GO film is transformed into a unitary graphene entity comprising or being a large-size graphene single crystal. This is a free-standing unitary graphene layer, which can be implemented directly as a heat spreader in an electronic device or used as a matrix material in a graphene matrix composite containing a carbon/graphite filler phase.

X-ray diffraction curves of a GO film (GO gel coated on a glass surface with liquid medium removed) prior to a heat treatment, a GO film thermally reduced at 150° C. for one hour, and a highly reduced and re-graphitized GO film (a unitary graphene layer) are shown in FIGS. 5( a), 5(b), and 5(c), respectively. The peak at approximately 20=12° of the dried GO film (FIG. 5( a)) corresponds to an inter-graphene spacing (d₀₀₂) of approximately 0.7 nm. With some heat treatment at 150° C., the GO film exhibits the formation of a hump centered at 22° (FIG. 5( b)), indicating that it has begun the process of decreasing the inter-graphene spacing, indicating the beginning of chemical linking and ordering processes. With a heat treatment temperature of 2,500° C. for one hour, the d₀₀₂ spacing has decreased to approximately 0.336, close to 0.3354 nm of a graphite single crystal.

With a heat treatment temperature of 2,750° C. for one hour, the d₀₀₂ spacing is decreased to approximately to 0.3354 nm, identical to that of a graphite single crystal. In addition, a second diffraction peak with a high intensity appears at 20=55° corresponding to X-ray diffraction from (004) plane (FIG. 5( d)). The (004) peak intensity relative to the (002) intensity on the same diffraction curve, or the I(004)/I(002) ratio, is a good indication of the degree of crystal perfection and preferred orientation of graphene planes. The (004) peak is either non-existing or relatively weak, with the I(004)/I(002) ratio <0.1, for all graphitic materials heat treated at a temperature lower than 2,800° C. The I(004)/I(002) ratio for the graphitic materials heat treated at 3,000-3,250° C. (e.g, highly oriented pyrolytic graphite, HOPG) is in the range of 0.2-0.5. One example is presented in FIG. 5( e) for a polyimide-derived PG with a HTT of 3,000° C. for two hours, which exhibits a I(004)/I(002) ratio of about 0.41. In contrast, a unitary graphene single crystal prepared with a HTT of 2,750° C. for one hour exhibits a I(004)/I(002) ratio of 0.78 and a Mosaic spread value of 0.21, indicating a practically perfect graphene single crystal with an exceptional degree of preferred orientation.

The “mosaic spread” value obtained from the full width at half maximum of the (002) reflection in an X-ray diffraction intensity curve. This index for the degree of ordering characterizes the graphite or graphene crystal size (or grain size), amounts of grain boundaries and other defects, and the degree of preferred grain orientation. A nearly perfect single crystal of graphite is characterized by having a mosaic spread value of 0.2-0.4. Most of our unitary graphene materials have a mosaic spread value in this range of 0.2-0.4 (with a heat treatment temperature no less than 2,000° C.).

It may be noted that the I(004)/I(002) ratio for all tens of flexible graphite samples investigated are all <<0.05, practically non-existing in most cases. The I(004)/I(002) ratio for all NGP paper/membrane samples is <0.1 even after a heat treatment at 3,000° C. for 2 hours. Attempts to graphitize the ultra-thin films (<2 nm in thickness) prepared by Cu-catalyzed CVD led to the breaking up of the film and the formation of graphite particles instead. These observations have further confirmed or affirmed the already established notion that the presently invented unitary graphene crystal is a new and distinct class of material that is fundamental different from any pyrolytic graphite (PG), flexible graphite (FG), and paper/film/membrane of conventional graphene/GO/RGO sheets/platelets (NGPs).

The inter-graphene spacing values of GO gel-derived unitary graphene films obtained by heat treating at various temperatures over a wide temperature range are summarized in FIG. 6( a). Corresponding oxygen content values in the GO gel-derived unitary graphene layer are shown in FIG. 6( b). In order to show the correlation between the inter-graphene spacing and the oxygen content, the data in FIGS. 6( a) and 6(b) are re-plotted in FIG. 6( c). A close scrutiny of FIG. 69( a)-(c) indicate that there are four HTT ranges (100-500° C.; 500-1,250° C.; 1,250-2,000° C., and >2,000° C.) that lead to four respective oxygen content ranges and inter-graphene spacing range. The thermal conductivity of GO gel-derived unitary graphene layer and corresponding flexible graphite (FG) foil, also plotted as a function of the same final heat treatment temperature range is summarized in FIG. 6( d).

It is of significance to point out that a heat treatment temperature as low as 500° C. is sufficient to bring the average inter-graphene spacing in GO to below 0.4 nm, getting closer and closer to that of natural graphite or that of a graphite single crystal. The beauty of this approach is the notion that this GO gel strategy has enabled us to re-organize, re-orient, and chemically merge the planar graphene oxide molecules from originally different graphite particles or graphene sheets into a graphene monolith with all the graphene planes now being larger in lateral dimensions (significantly larger than the length and width of original graphene planes) and essentially parallel to one another. This has given rise to a thermal conductivity already >420 W/mK (with a HTT of 500° C.) and >950 W/mk with a HTT of 700° C.), which is more than 2-to 4-fold greater than the value (200 W/mK) of the corresponding flexible graphite foil. These planar GO molecules are derived from the graphene planes that constitute the original structure of starting natural graphite particles (used in the procedure of graphite oxidation to form the GO gel). The original natural graphite particles, when randomly packed into an aggregate or “graphite compact”, would have their constituent graphene planes randomly oriented, exhibiting relatively low thermal conductivity and having essentially zero strength (no structural integrity). In contrast, the strength of the unitary graphene layer (even without an added reinforcement) is typically already in the range of 40-140 MPa.

With a HTT as low as 800° C., the resulting unitary graphene layer exhibits a thermal conductivity of 1,148 W/mK, in contrast to the observed 244 W/mK of the flexible graphite foil with an identical heat treatment temperature. As a matter of fact, no matter how high the HTT is (e.g. even as high as 2,800° C.), the flexible graphite foil only shows a thermal conductivity lower than 600 W/mK. At a HTT of 2,800° C., the presently invented unitary graphene layer delivers a thermal conductivity of 1,807 W/mK (FIG. 4( a) and FIG. 6( d)).

Scanning electron microscopy (SEM), transmission electron microscopy (TEM) pictures of lattice imaging of the graphene layer, as well as selected-area electron diffraction (SAD), bright field (BF), and dark-field (DF) images were also conducted to characterize the structure of unitary graphene materials. For measurement of cross-sectional views of the film, the sample was buried in a polymer matrix, sliced using an ultra-microtome, and etched with Ar plasma.

A close scrutiny and comparison of FIGS. 2( a), 3(a), and 3(b) indicates that the graphene layers in a graphene single crystal or graphene monolithic are substantially oriented parallel to one another; but this is not the case for flexible graphite foils and graphene oxide paper. The inclination angles between two identifiable layers in the unitary graphene entity are mostly less than 5 degrees. In contrast, there are so many folded graphite flakes, kinks, and mis-orientations in flexible graphite that many of the angles between two graphite flakes are greater than 10 degrees, some as high as 45 degrees (FIG. 2( b)). Although not nearly as bad, the mis-orientations between graphene platelets in NGP paper (FIG. 3( b)) are also high and there are many gaps between platelets. The unitary graphene entity is essentially gap-free.

FIG. 4 (a) shows the thermal conductivity values of the GO gel-derived unitary graphene matrix layer (▴), GO platelet paper (▪) prepared by vacuum-assisted filtration of RGO, and FG foil (♦), respectively, all plotted as a function of the final HTT for graphitization or re-graphitization. These data have clearly demonstrated the superiority of the unitary graphene material or graphene single crystal in terms of the achievable thermal conductivity at a given heat treatment temperature. All the prior art work on the preparation of paper or membrane from pristine graphene or graphene oxide sheets/platelets follows distinctly different processing paths, leading to a simple aggregate or stack of discrete graphene/GO/RGO platelets. These simple aggregates or stacks exhibit many folded graphite flakes, kinks, gaps, and mis-orientations, resulting in poor thermal conductivity, low electrical conductivity, and weak mechanical strength. As shown in FIG. 4( a), even at a heat treatment temperature as high as 2,800° C., the GO platelet paper exhibits a thermal conductivity less than 1,000 W/mK, much lower than the >1,800 W/mK of the GO gel-derived unitary graphene entity.

For comparison, we have also carbonized polyimide films at 500° C. for 1 hour and at 1,000° C. for 3 hours in an inert atmosphere and then graphitized the films at a temperature in the range of 2,500-3,000° C. for 1 to 5 hours to form a conventional pyrolytic graphite (PG) film. FIG. 4( b) shows the thermal conductivity values of the GO-derived unitary graphene (▪) and the polyimide-derived PG heat-treated for one hour (x) and for 3 hours (▴), all plotted as a function of the final graphitization or re-graphitization temperature. These data show that the conventional PG, produced by carbonizing polyimide (PI) and then graphitizing the carbonized PI, exhibits a consistently lower thermal conductivity as compared to the GO gel-derived unitary graphene alone (▪), given the same HIT for the same length of heat treatment time. For instance, the PG from PI exhibits a thermal conductivity of 820 W/mK after a graphitization treatment at 2,000° C. for one hour and 1,242 W/mK at 2,000° C. for 3 hours. These observations have demonstrated a clear and significant advantage of using the GO gel approach to producing unitary graphene materials versus the conventional PG approach to producing oriented graphite crystals. As a matter of fact, no matter how long the graphitization time is for the PG, the thermal conductivity is always lower than that of a GO gel-derived unitary graphene. In other words, the unitary graphene material is fundamentally different and patently distinct from the flexible graphite (FG) foil, graphene/GO/RGO paper/membrane, and pyrolytic graphite (PG) in terms of chemical composition, crystal and defect structure, crystal orientation, morphology, process of production, and properties.

The above conclusion is further supported by the data in FIG. 4( c) showing the electric conductivity values of the GO-derived unitary graphene layer (♦) are far superior to those of the GO paper (▪) from RGO platelets and FG foil (x) over the entire range of final HTTs investigated.

EXAMPLES 5 Preparation and Testing of Unitary Graphene Matrix Composites

GO gel can be combined with a carbon/graphite filler phase to form a graphene matrix composite. The graphene oxide gel prepared in Example 4 was used for the preparation of graphene matrix composite. The exfoliated graphite flakes prepared in Examples 1 were made into thin porous paper or film form (e.g., using a vacuum-assisted filtration technique) for use as a carbon/graphite filler. Other carbon or graphite fillers investigated include carbon nano-tubes and CNT paper (Bucky paper from Buckeye Composites, Inc., Dayton, Ohio), carbon nano-fibers and CNF mats (CNFs supplied from Applied Sciences, Inc., Cedarville, Ohio), flexible graphite foils of several different thicknesses (supplied from Graftech and Timcal Graphite), carbon fibers and carbon fiber mats, woven fabrics of graphite fibers, carbon paper (Toray), MCMB particles, carbon black (CB), acetylene black (AB), and needle coke.

As examples, two approaches were adapted to produce graphene matrix composites. In the first approach, the particles of the carbon/graphite filler phase were formed into porous pre-forms, such as porous paper, mat, and fabric (woven or non-woven). The porous pre-form was then impregnated with GO gel, which was followed by drying and heat treating.

In a second approach, discrete particles or fibers of the carbon/graphite filler phase were added into the GO gel to form a mixture gel or gel slurry. Pure GO gel or carbon/graphite filler-GO mixture gel or slurry was then cast onto a solid substrate surface using a coating machine equipped with drying and heating provisions. In some cases, the GO gel or filler-GO gel mixture was cast onto a substrate and regulated by a doctor's blade to form a uniform coating thereon. This procedure creates a shear stress field that induces viscosity thinning and molecular orientation. The liquid in the coating was further removed in a vacuum oven to form a solid GO coating. The resulting GO or GO-filler layers were then subjected to a heat treatment at a temperature of from 100° C. up to approximately 3,000° C. We have utilized several temperature regimes: 100° C.-500° C.; 500° C.-1,250° C.; 1,250° C.-2,000° C.; and 2,000° C.-3,000° C.

EXAMPLES 6 Electrical and Thermal Conductivity Measurements of Various Graphene Oxide-Derived Unitary Graphene and Graphene Matrix Composite Layers

Four-point probe tests were conducted on unitary graphene matrix composites (e.g. containing CNT, expanded graphite flakes, carbon black, etc), the GO gel-derived unitary graphene layer alone (coated on a glass surface and then peeled off and heat treated), GO/RGO paper, and the FG foils alone to measure their in-plane electrical conductivity. Their in-plane thermal conductivity was measured using a laser flash method (Netzsch Thermal Diffusivity Device).

The in-plane thermal and electrical conductivities and tensile properties of various films or laminates were investigated. Several significant observations can be made from the testing results (e.g. as summarized in FIGS. 4( d), 4(e), 7(a), 7(b), 8(a), and 8(b)):

-   -   (1) With a thickness of approximately 75 μm, the thermal         conductivity of the flexible graphite foil alone (FG, ▴ in FIG.         4( a)) is less than 237 W/mK if the FG foil is not heat-treated         at or above 700° C. As the post-recompression heat treatment         temperature increases from 700° C. to 2,800° C. (for one hour of         graphitization treatment in each case), the thermal conductivity         of the FG foil increases from 237 to 582 W/mK, indicating some         but limited re-organization of the graphitic structure induced         by the heat treatment. By contrast, the thermal conductivity of         the GO gel-derived unitary graphene layer alone increases from         983 to 1,807 W/mK (▪ in FIG. 7( a)). This unitary graphene         matrix material is obtained by shearing and depositing a layer         of GO gel on a glass surface, removing the liquid from the GO         layer in vacuum for 1 hour, and peeling off the dried solid GO         layer from the glass surface. This indicates a significant or         dramatic re-organization of the graphitic structure induced by         the heat treatment, with all GO molecules linked or merged         edge-to-edge and face-to-face into a unitary graphene body of         fully and orderly bonded graphene planes, a graphene single         crystal.     -   (2) The experimentally measured thermal conductivity of a         corresponding series of GO gel-derived unitary graphene matrix         composite containing expanded graphite flakes as the filler         phase (♦ in FIG. 7( a)) increases from approximately 800 to         1,800 W/mK. This is significantly higher than the thermal         conductivity values of what would be theoretically predicted (x         in FIG. 7 a)) from a rule-of-mixture law, which is commonly used         to predict composite properties from constituent properties.         These data have clearly demonstrated an un-expected, synergistic         effect between GO gel-derived unitary graphene matrix (derived         from graphene oxide gel) and the dispersed expanded graphite         flakes.

Also shown in FIG. 7( a) are the thermal conductivity data of corresponding flexible graphite foil (FG prepared by roll-pressing of exfoliated graphite worms) and foil or mat of expanded graphite flakes (prepared by breaking up graphite worms into graphite flakes as described in Example 1, which were then packed and roll-pressed into a thin foil/mat). The highest thermal conductivity value achievable with the expanded graphite foil is <800 W/mK and that with FG is <600 W/mK, both being dramatically lower than those of both the unitary graphene matrix and the graphene matrix composite.

-   -   (3) FIG. 7( b) shows that the conventional PG, produced by         carbonizing polyimide, roll-pressing, and then graphitizing the         carbonized PI, exhibits a consistently lower thermal         conductivity as compared to the GO gel-derived unitary graphene         layer alone (▪) or unitary graphene matrix composite (♦), given         the same HTT for the same length of heat treatment time. For         instance, the PG from PI exhibits a thermal conductivity of 820         W/mK after a graphitization treatment at 2,000° C. for one hour         and 1,242 W/mK at 2,000° C. for 3 hours. These observations have         demonstrated a clear and significant advantage of using the GO         gel approach versus the conventional PG approach. As a matter of         fact, no matter how long the graphitization time is for the PG,         the thermal conductivity is always lower than that of a GO         gel-derived unitary graphene or unitary graphene matrix         composite. These observations have clearly further validate the         notion that both the GO gel-derived unitary graphene layer and         unitary graphene matrix composite are fundamentally different         and patently distinct from the pyrolytic graphite in terms of         chemical composition, structure, morphology, process of         production, and properties.     -   (4) FIG. 4( d) shows the thermal conductivity values of both         unitary graphene matrix and graphene matrix-CNT composite are         far superior to those of prior art GO platelet paper containing         discrete GO platelets and those of GO platelet paper containing         an equal proportion of the same CNTs (approximately 26% by         weight). FIG. 4( e) demonstrates that unitary graphene matrix         composite containing carbon black particles as the         carbon/graphite filler phase are significantly higher than those         of prior art GO paper and corresponding GO-CB paper.

EXAMPLES 7 Tensile Strength of Various Graphene Oxide-Derived Unitary Graphene Matrix Composites

A series of GO gel-derived unitary graphene layers, graphene matrix composites, GO platelet paper, and FG foil were prepared. A universal testing machine was used to determine the tensile strength of these materials. The tensile strength values of the unitary graphene entity, GO platelet paper, and FG paper are plotted as a function of the re-graphitization temperature, FIG. 8( a). These data have demonstrated that the tensile strength of the flexible graphite foil remains relatively constant (all <20 MPa) and that of the GO paper increases slightly (from 22 to 43 MPa) when the heat treatment temperature increases from 700 to 2,800° C. In contrast, the tensile strength of the GO-derived unitary graphene layer increases dramatically from 32 to >100 MPa over the same range of heat treatment temperatures. This result is quite striking and further reflects the notion that the GO gel-derived GO layer contains highly live and active molecules during the heat treatment, while the graphene platelets in the conventional GO paper and the graphite flakes in the FG foil are essentially dead molecules. The GO-derived unitary graphene entity or graphene single crystal is a class of material by itself.

The tensile strength values of three unitary graphene matrix composites with the final re-graphitization temperature of 1,500° C. are plotted as a function of the filler weight fraction for three carbon/graphite filler types: CNT, expanded graphite flakes, and carbon black particles (FIG. 8( b)). Although adding CNTs to the unitary graphene matrix decreases the thermal conductivity (FIG. 4( d)), the strength of the resulting composites increases monotonically with (actually proportional to) the CNT weight fraction, reaching a value of 200 MPa that is one order of magnitude higher than the typical strength of flexible graphite-type materials. This is completely unexpected.

This suggests that GO molecules have a strong adhering power capable of bonding to CNTs, creating a strong interfacial bond to assist in the load transfer and enabling CNTs to carry a significant proportion of the mechanical force imposed upon the composite. It may be noted that epoxy matrix composites containing multi-walled carbon nanotubes as the reinforcement phase have never exhibit a tensile strength higher than 80 MPa. This is partially due to the difficulty of dispersing CNTs in a polymer, to the extent that it has been extremely difficult to well-disperse more than 5% by weight of CNTs in epoxy. Beyond 5% by weight, CNTs could not be homogeneously dispersed in epoxy and the tensile strength actually begins to decrease with increasing CNT weight percentage. The observation that CNTs can be well dispersed in the graphene matrix up to 30% by weight is shocking, indicating outstanding chemical compatibility between GO molecules and discrete CNT filaments. Further shocking is the 200 MPa tensile strength exhibited by the graphene matrix-CNT composite, a value that no reinforced epoxy composite has been able to achieve unless the reinforcement phase (such as high-strength carbon fibers) is well aligned in the loading direction (e.g. in a unidirectional fiber composite).

EXAMPLES 8 The Surface Scratch Resistance in Terms of Scratch Visibility and Scratch Depth, and Hardness of Various Unitary Graphene Matrix Composites

The scratch test was conducted using the so-called Ford Lab Test Method (FLTM) BN108-13. This apparatus consists of a movable platform connected to five beams with 250 mm in length. A scratch pin is attached to one end of each beam. A highly polished hardened steel ball (1.0±0.1 nun diameter) is placed on the tip of each pin. Each pin is loaded with a weight that exerts a force of 7 N, 6 N, 3 N, 2 N, and 0.6 N, respectively. Driven by compressed air, the beams draw the pins across the specimen surface and generate scratches. The scratch is made at a sliding velocity of approximately 100 mm/s. All tests were performed at room temperature. Although the test method requires that grained surfaces be evaluated, only the smooth surfaces of the specimens were tested in this study.

After the specimen plaques were scratched, they were evaluated with a reflected light polarizing microscope incorporating a Xenon light source. An image analyzer with Image Analysis Software was used to measure the “gray scale mass,” which is the total gray scale value of the object. The camera objective lens is positioned at an angle of 90° from the scratch. The objective lens then registers a portion of the scratch about 1 mm long. The electron signal for each scratch line is then integrated and recorded. The optical mass of an object, M, is the sum of the gray level values, GL, of all pixels in the object. The individual gray level values are assigned by the image analysis program in unit steps in the range of 0-255, where 0=black and 255=white. The optical mass, M, can be computed from: M=ΣGL_(i) (sum over i to n), where n is the number of pixels. The brightness of the object, B, is B=M/A, where A represents the area of the object. The percentage change in the brightness between the scratch and the background is the scratch visibility, ΔB, given by ΔB=[(B_(scratch)−B_(background))/(B_(background))]×100%. The depth of the scratch was measured using an interferometer. The magnification was set at 5×. Depth measurements were made from the depth histogram of the scanned area. The scratches were also examined using a scanning electron microscope (SEM).

Indentation hardness tests were also performed on selected specimens. For the Rockwell Hardness test, the ASTM D 785 test procedure was followed. The indenter was a round steel ball with 12.5 mm in diameter (Rockwell R scale). The Rockwell hardness number is a measure of the non-recoverable indentation after a heavy load of 588 N for a period of 15 s, and subsequently reduced to a minor load of 98 N for another duration of 15 s. Normal hardness is then defined as the load divided by the projected area.

FIGS. 8( c) and 8(d) show the Rockwell hardness and scratch depth data, respectively, of several graphene matrix composites plotted as a function of the filler weight percentage (FIG. 8( c)) and re-graphitization temperature (FIG. 8( d)). The Rockwell hardness data in FIG. 8( c) are found to be well correlated with the tensile strength data of FIG. 8( b). Again, the presence of CNTs can significantly increase the hardness of the unitary graphene matrix. The scratch resistance of the unitary graphene matrix can also be significantly improved by adding some CNT (20% by weight as in FIG. 8( d)). This improvement is diminished as the final re-graphitization temperature exceeds 1,000 C wherein the unitary graphene matrix alone is already of high strength and hardness.

EXAMPLES 9 Thermal and Electrical Properties of Various Unitary Graphene Matrix Composites

The thermal and electric conductivities of unitary graphene matrix composites containing various carbon or graphite fillers in different forms are summarized in Table 1 below. Given the same final heat treatment temperature, all the graphene matrix composites exhibit better electric and thermal conductivities as compared to the baseline flexible graphite foil and GO paper.

TABLE 1 In-plane thermal and electric conductivities Re-graphi- Thermal Electric tization temp- conduc- conduc- erature Filler type, tivity tivity Sample No. (° C.) form, and wt. % (W/mK) (S/cm) 31-G 1,500 None 1,610 4,200 31-G-AB 1,500 Acetylene black 946 3,550 particles, dispersed, 35% 31-G-MCMB 1,500 Particles, dispersed, 1,156 3,605 25% 31-G-Coke 1,500 Needle coke, dispersed, 1,028 3,002 25% 32-G 2,500 None 1,736 10,300 32-G-CNF 2,500 CNF, mat, 10% 1,550 9,213 32-G-CF-Uni 2,500 Continuous carbon 1,250 7,250 fibers, unidirec- tional, 55% 32-G-CF-W 2,500 Continuous carbon 1,143 6,037 fibers, woven fabric, 54% 32-G-CF-Ch 2,500 Chopped carbon fiber, 1,057 5,454 mat, 45% 32-G-AC 2,500 Activated carbon, 1,611 9,763 dispersed, 15% FG foil 2,500 — 560 2,300 GO paper 2,500 — 920 3,500

As indicated in FIGS. 7( a) and 7(b), the presently invented unitary graphene matrix composites do not have to go through an ultra-high-temperature graphitization treatment to achieve a high thermal conductivity (e.g. K already=988 W/mK with T=800° C. and K=1,487 W/mK with T=1,250° C.). Graphitization of a carbonized resin (e.g. polyimide) or other carbon materials requires a temperature typically higher than 2,000° C., most typically higher than 2,500° C. The graphitization temperature is most typically in the range of 2,800-3,200° C. in order for carbonized materials or pyrolytic graphite to achieve a thermal conductivity of 1,600-1,700 W/mK. In contrast, the typical heat treatment temperature (re-graphitization treatment) of the presently invented GO-coated laminates is significantly lower than 2,500° C. and more typically lower than 1,500° (can be as lower than 500° C.).

For instance, polyimide (PI), if carbonized and graphitized for 5 hours (including 4 hours for carbonization at 1,000-1,500° C. and 1 hour for graphitization at 2,000° C.), exhibits a thermal conductivity of 820 W/mK. In contrast, we were able to reach a thermal conductivity of 988 W/mK with a heat treatment of graphene matrix composite at 800° C. for a total of two hours. This is very surprising and no one has ever thought that such a low graphitization temperature was possible. Further, a heat treatment of the GO gel-derived unitary graphene-matrix composite at the same 2,000° C. for 1 hour imparts a thermal conductivity of 1,680 W/mK (vs. 820 W/mK of the carbonized PI). Clearly, this is a dramatically faster, less energy-intensive, and more cost-effective process. The resulting products are also far superior to pyrolytic graphite. The unitary graphene matrix composites, the unitary graphene layer itself (from GO gel), and the pyrolytic graphite are three fundamentally different and patently distinct classes of materials in terms of chemical composition, morphology, structure, process of production, and various properties.

In conclusion, we have successfully developed an absolutely new, novel, unexpected, and patently distinct class of highly conducting material: graphene oxide gel-derived unitary graphene material and unitary graphene matrix composite. The chemical composition, structure (crystal perfection, grain size, defect population, etc), crystal orientation, morphology, process of production, and properties of this new class of materials are fundamentally different and patently distinct from flexible graphite foil, polymer-derived pyrolytic graphite, CVD-derived PG (including HOPG), and catalytic CVD graphene thin film. The thermal conductivity, electrical conductivity, scratch resistance, surface hardness, and tensile strength exhibited by the presently invented materials are much higher than what prior art flexible graphite sheets, paper of discrete graphene/GO/RGO platelets, or other graphitic films could possibly achieve. These GO-derived unitary graphene materials have the best combination of excellent electrical conductivity, thermal conductivity, mechanical strength, surface scratch resistance, hardness, and no tendency to flake off. 

We claim:
 1. A process for producing a unitary graphene material, said process comprising: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium wherein said graphene oxide molecules contain an oxygen content higher than 20% by weight; (b) dispensing and depositing a layer of said graphene oxide gel onto a surface of a supporting substrate to form a deposited graphene oxide gel thereon, wherein said dispensing and depositing procedure includes shear-induced thinning of said graphene oxide gel; (c) partially or completely removing said fluid medium from the deposited graphene oxide gel to form a graphene oxide mass having an inter-plane spacing d₀₀₂ of 0.4 nm to 1.2 nm as determined by X-ray diffraction and an oxygen content no less than 20% by weight; and (d) heat treating the graphene oxide mass to form said unitary graphene material at a heat treatment temperature higher than 100° C. to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.4 nm and the oxygen content is decreased to less than 5% by weight.
 2. The process of claim 1, wherein step (c) includes forming a graphene oxide mass having an inter-plane spacing d₀₀₂ of 0.4 nm to 0.7 nm and an oxygen content no less than 20% by weight; and step (d) includes heat-treating the graphene oxide mass to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.36 nm and the oxygen content is decreased to less than 2% by weight.
 3. The process of claim 1, wherein said graphene oxide gel has a viscosity greater than 2,000 centipoise when measured at 20° C. prior to said shear-induced thinning and the viscosity is reduced to less than 2,000 centipoise during or after shear-induced thinning.
 4. The process of claim 1, wherein said graphene oxide gel has a viscosity from 500 centipoise to 500,000 centipoise when measured at 20° C. prior to said shear-induced thinning.
 5. The process of claim 1, wherein said graphene oxide gel has a viscosity no less than 5,000 centipoise when measured at 20° C. prior to said shear-induced thinning and the viscosity is reduced to less than 2,000 centipoise during or after shear-induced thinning.
 6. The process of claim 1, wherein said graphene oxide gel has a viscosity that decreases by at least 10 times when a shear rate is increased at 20° C.
 7. The process of claim 1, wherein shear-induced thinning is conducted via a procedure selected from coating, casting, injection molding, compression molding, resin-transfer molding, extrusion, pultrusion, filament winding.
 8. The process of claim 1, wherein said step (d) includes heat treating said graphene oxide mass under a compressive stress.
 9. The process of claim 1, wherein said unitary graphene material has a thickness greater than 100 nm.
 10. The process of claim 1, wherein said unitary graphene material has a thickness greater than 100 nm but less than 10μm.
 11. The process of claim 1, wherein said unitary graphene material has a thickness greater than 10 μm.
 12. The process of claim 1, wherein said unitary graphene material has a thickness greater than 100 μm.
 13. The process of claim 1, wherein said graphene oxide gel is prepared by immersing a graphitic material in a powder or fibrous form in an oxidizing liquid to form an initially optically opaque and dark suspension in a reaction vessel at a reaction temperature for a length of time sufficient to obtain a graphene oxide gel that is a homogeneous solution and also optically transparent, translucent, or brown-colored, wherein said graphene oxide gel is composed of graphene oxide molecules dissolved in an acidic medium having a pH value of no higher than 5 and said graphene oxide molecules have an oxygen content no less than 20% by weight.
 14. The process of claim 1, wherein said graphene oxide gel is prepared by immersing a graphitic material in an oxidizing agent to form an initially optically opaque and dark suspension and allowing an oxidizing reaction to proceed until a homogeneous and optically transparent, translucent, or brown-color solution is formed, and wherein said graphitic material is selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof.
 15. The process of claim 1, wherein said steps (b) and (c) include feeding a sheet of a solid substrate material from a roller to a deposition zone, depositing a layer of graphene oxide gel onto a surface of said sheet of solid substrate material to form a graphene oxide gel layer thereon, drying said graphene oxide gel to form a dried graphene oxide layer deposited on said substrate surface, and collecting graphene oxide layer-deposited substrate sheet on a collector roller.
 16. The process of claim 1, wherein the unitary graphene material further contains a discrete solid carbon, graphite, or graphene filler phase dispersed in said unitary graphene material to form a unitary graphene matrix composite structure and said filler phase is selected from a carbon or graphite fiber, carbon or graphite nano-fiber, carbon nano-tube, carbon nano-rod, meso-phase carbon particle, meso-carbon micro-bead, expanded graphite flake with a thickness greater than 100 nm, single-layer graphene sheet, multi-layer graphene platelet with a thickness less than 100 nm, exfoliated graphite or graphite worm, coke particle, needle coke, carbon black or acetylene black particle, activated carbon particle, or a combination thereof; wherein said carbon, graphite, or graphene filler phase occupies a weight fraction of 0.01% to 99% based on the total composite structure weight.
 17. The process of claim 16, wherein said carbon, graphite, or graphene filler phase is chemically bonded by said unitary graphene matrix.
 18. The process of claim 16, wherein said unitary graphene matrix composite has a physical density of at least 1.8 g/cm³ or a porosity level lower than 5%.
 19. The process of claim 1, wherein said heat treatment temperature contains a temperature in a thermal reduction regime of 100° C.-500° C. and the unitary graphene material has an oxygen content less than 5%, an inter-graphene spacing less than 0.4 nm, and/or a thermal conductivity of at least 100 W/mK.
 20. The process of claim 1, wherein said heat treatment temperature contains a temperature in the range of 500° C.-1,250° C. and the unitary graphene material has an oxygen content less than 1%, an inter-graphene spacing less than 0.345 nm, a thermal conductivity of at least 1,300 W/mK, and/or an electrical conductivity no less than 3,000 S/cm.
 21. The process of claim 1, wherein said heat treatment temperature contains a temperature in the range of 1,250° C.-2,000° C. and the unitary graphene material has an oxygen content less than 0.01%, an inter-graphene spacing less than 0.337 nm, a thermal conductivity of at least 1,500 W/mK, and/or an electrical conductivity no less than 5,000 S/cm.
 22. The process of claim 1, wherein said heat treatment temperature contains a temperature greater than 2,000° C. and the unitary graphene material has an oxygen content no greater than 0.001%, an inter-graphene spacing less than 0.336 nm, a mosaic spread value no greater than 0.7, a thermal conductivity of at least 1,700 W/mK, and/or an electrical conductivity no less than 10,000 S/cm.
 23. The process of claim 1, wherein said heat treatment temperature contains a temperature no less than 2,500° C. and the unitary graphene material has an inter-graphene spacing less than 0.336 nm, a mosaic spread value no greater than 0.4, a thermal conductivity greater than 1,700 W/mK, and/or an electrical conductivity greater than 10,000 S/cm.
 24. The process of claim 1, wherein the unitary graphene material exhibits an inter-graphene spacing less than 0.337 nm and a mosaic spread value less than 1.0.
 25. The process of claim 1, wherein the unitary graphene material exhibits a degree of graphitization no less than 40% and/or a mosaic spread value less than 0.7.
 26. The process of claim 1, wherein the unitary graphene material exhibits a degree of graphitization no less than 80% and/or a mosaic spread value no greater than 0.4.
 27. The process of claim 1, wherein said unitary graphene material contains chemically bonded graphene molecules or chemically merged graphene planes that are parallel to one another.
 28. The process of claim 1, wherein said unitary graphene material contains no complete grain boundary therein, is a graphene single crystal, or a poly-crystal graphene structure with graphene molecules being oriented along a preferred direction.
 29. The process of claim 1, wherein said graphene oxide gel is obtained from a graphitic material having a maximum original graphite grain size and said unitary graphene material is a single crystal or a poly-crystal graphene structure having a grain size larger than said maximum original grain size.
 30. The process of claim 1, wherein said graphene oxide gel is obtained from a graphitic material having multiple graphite crystallites exhibiting no preferred crystalline orientation as determined by an X-ray diffraction or electron diffraction method and wherein said unitary graphene material is a single crystal or a poly-crystal graphene structure having a preferred crystalline orientation as determined by said X-ray diffraction or electron diffraction method.
 31. The process of claim 1, wherein said unitary graphene material contains a combination of sp² and sp³ electronic configurations.
 32. The process of claim 1, wherein said graphene oxide gel is obtained by immersing a graphitic material in a powder or fibrous form in an oxidizing liquid medium in a reaction vessel at a reaction temperature for a length of time sufficient to obtain a homogeneous solution composed of graphene oxide molecules dissolved in the liquid medium, wherein said homogeneous solution is optically transparent, translucent, or brown colored and said graphene oxide molecules have an oxygen content no less than 20% by weight and a molecular weight less than 43,000 g/mole while in a gel state.
 33. The process of claim 32, wherein said graphene oxide molecules have a molecular weight less than 4,000 g/mole while in a gel state.
 34. The process of claim 32, wherein said graphene oxide molecules have a molecular weight between 200 g/mole and 4,000 g/mole while in a gel state.
 35. The process of claim 1, wherein said step of heat-treating induces chemical linking, merging, or chemical bonding of graphene oxide molecules, and/or re-graphitization or re-organization of a graphitic structure.
 36. The process of claim 1, wherein said unitary graphene material has an electrical conductivity greater than 3,000 S/cm, a thermal conductivity greater than 600 W/mK, a physical density greater than 1.8 g/cm3, and/or a tensile strength greater than 40 MPa.
 37. The process of claim 1, wherein said unitary graphene material has an electrical conductivity greater than 5,000 S/cm, a thermal conductivity greater than 1,000 W/mK, a physical density greater than 1.9 g/cm3, and/or a tensile strength greater than 60 MPa.
 38. The process of claim 1, wherein said unitary graphene material has an electrical conductivity greater than 15,000 S/cm, a thermal conductivity greater than 1,500 W/mK, a physical density greater than 2.0 g/cm³, and/or a tensile strength greater than 80 MPa.
 39. A process for producing a unitary graphene matrix composite, said process comprising: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium to form a homogeneous solution; (b) mixing a carbon or graphite filler phase in the graphene oxide gel to form a slurry; (c) dispensing the slurry into a cavity of a molding tool or forming the slurry into a desired shape under the influence of a shear stress to create shear-induced thinning and molecular orientation; (d) partially or completely removing the fluid medium from the slurry to form a composite precursor comprising a graphene oxide matrix material having an inter-plane spacing d₀₀₂ of 0.4 nm to 1.2 nm as determined by X-ray diffraction and an oxygen content no less than 20% by weight; and (e) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.4 nm and the oxygen content is decreased to less than 5% by weight.
 40. A process for producing a unitary graphene matrix composite, said process comprising: (a) preparing a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium to form a homogeneous solution; (b) combining a carbon or graphite filler phase with said graphene oxide gel to form an impregnated filler shape under the influence of a shear stress that induces viscosity thinning; (c) partially or completely removing the fluid medium from the impregnated filler shape to form a composite precursor comprising a graphene oxide matrix material having an inter-plane spacing d₀₀₂ of 0.4 nm to 1.2 nm as determined by X-ray diffraction and an oxygen content no less than 20% by weight; and (d) heat-treating the composite precursor to form the unitary graphene composite at a temperature higher than 100° C. to an extent that an inter-plane spacing d₀₀₂ is decreased to a value of from 0.3354 nm to 0.4 nm and the oxygen content is decreased to less than 5% by weight. 